U.S. patent application number 11/648418 was filed with the patent office on 2007-08-23 for decorative solar control laminates.
Invention is credited to Richard A. Hayes, Rebecca L. Smith.
Application Number | 20070196630 11/648418 |
Document ID | / |
Family ID | 38428573 |
Filed Date | 2007-08-23 |
United States Patent
Application |
20070196630 |
Kind Code |
A1 |
Hayes; Richard A. ; et
al. |
August 23, 2007 |
Decorative solar control laminates
Abstract
The present invention provides decorative laminates having the
benefits of solar control laminates and processes for producing
same. Laminates of the present invention comprise a polymer sheet
having upper and lower surfaces, said sheet having a thickness of
at least about 0.25 mm, said polymer having a modulus of between
about 20,000 psi (138 MPa) and about 100,000 psi (690 MPa), as
determined according to ASTM D 638-03, at least one of said
surfaces of said sheet having disposed thereon an image, a film
layer and, optionally, an adhesive composition, at least a portion
of said adhesive composition being in contact with said image.
Inventors: |
Hayes; Richard A.;
(Beaumont, TX) ; Smith; Rebecca L.; (Vienna,
WV) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
38428573 |
Appl. No.: |
11/648418 |
Filed: |
December 29, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60755248 |
Dec 30, 2005 |
|
|
|
Current U.S.
Class: |
428/195.1 |
Current CPC
Class: |
B32B 17/10247 20130101;
B32B 17/10743 20130101; B32B 17/10018 20130101; Y10T 428/24802
20150115; B32B 17/10761 20130101; B32B 17/10174 20130101; B32B
17/10275 20130101; B32B 2367/00 20130101; B32B 17/10036 20130101;
B32B 17/10005 20210101; B32B 2367/00 20130101 |
Class at
Publication: |
428/195.1 |
International
Class: |
B44C 1/17 20060101
B44C001/17 |
Claims
1. A laminate comprising (1) at least one layer comprising a
polymer sheet having upper and lower surfaces, said polymer sheet
having a thickness of at least about 0.25 mm and comprising a
polymer composition having a modulus of between about 20,000 psi
(138 MPa) and about 100,000 psi (690 MPa), at least one of said
surfaces of said sheet having disposed thereon an image and (2) at
least one layer of a film.
2. The laminate of claim 1, said polymer composition having a
modulus of between about 25,000 psi (173 MPa) and about 90,000 psi
(621 MPa), as determined according to ASTM D 638-03.
3. The laminate of claim 2, said polymer composition having a
modulus of between about 30,000 psi (207 MPa) and about 80,000 psi
(552 MPa), as determined according to ASTM D 638-03.
4. The laminate of claim 3, said polymer composition comprising one
or more of an ethylene acid copolymer or ionomer, a vinyl chloride
polymer or copolymer, and a polyurethane.
5. The laminate of claim 4, said polymer composition comprising an
ethylene acid copolymer or ionomer.
6. The laminate of claim 1, wherein at least one image is disposed
on each of said upper and lower surfaces of said polymer sheet.
7. The laminate of claim 1, wherein said image is disposed on at
least ten percent of the surface of at least one of said surfaces
of said sheet.
8. The laminate of claim 1, wherein the polymer sheet has a
thickness of at least about 0.38 mm.
9. The laminate of claim 1, wherein the polymer sheet has a
thickness of at least about 0.75 mm.
10. The laminate of claim 1, wherein the image is formed by one or
more inks.
11. The laminate of claim 10, wherein the percent coverage of the
surface by the one or more inks is at least ten percent.
12. The laminate of claim 10, wherein one or more of the inks
comprises an adhesive composition.
13. The laminate of claim 10, wherein one or more of the inks
comprises at least one pigment selected from the group consisting
of: PY 120; PY 155; PY 128; PY 180; PY95; PY 93; PV19; PR 202; PR
122; PB 15:4; PB 15:3; and PBI 7.
14. The laminate of claim 10, wherein one or more of the inks is
applied to the at least one surface of the polymer sheet using an
ink-jet printing device.
15. The laminate of claim 1, that further comprises an adhesive
composition, wherein at least a portion of said adhesive
composition is in contact with said image.
16. The laminate of claim 15, wherein the adhesive composition
comprises a material selected from the group consisting of
gamma-aminopropyltriethoxysilane,
N-beta-(aminoethyl)-gamma-aminopropyl-trimethoxysilane and
combinations thereof.
17. The laminate of claim 1, wherein the adhesive is a coating
having a thickness of 0.026 mm or less.
18. The laminate of claim 17, wherein the adhesive is a coating
having a thickness of 0.013 mm or less.
19. The laminate of claim 18, wherein the adhesive is a coating
having a thickness of 0.0026 mm or less.
20. The laminate of claim 15, wherein the adhesive composition is
disposed on one hundred percent of the at least one image-bearing
surface.
21. The laminate of claim 1, wherein the film is a biaxially
oriented poly(ethylene terephthalate) film.
22. The laminate of claim 1, wherein the film is a solar control
film.
23. The laminate of claim 22, wherein the solar control film
comprises: indium tin oxide; antimony tin oxide; or lanthanum
hexaboride.
24. The laminate of claim 22, wherein the solar control film is an
IR-reflective film.
25. A process for producing the laminate of claim 1 comprising the
steps of: (1) forming an image-bearing surface on a polymer sheet
by applying an image to at least one surface of a polymer sheet
having upper and lower surfaces, said sheet having a thickness of
at least about 0.25 mm, said polymer having a modulus of between
about 20,000 psi (138 MPa) and about 100,000 psi (690 MPa), as
determined according to ASTM D 638-03; (2) optionally applying an
adhesive composition to at least a portion of said image-bearing
surface; and (3) laminating the image-bearing surface to at least
one film layer.
26. The process of claim 25, wherein the film has been treated to
enhance adhesion.
27. The process of claim 26, wherein the film has been treated with
adhesives, primers, silanes, poly(allyl amine), flame treatments,
plasma treatments, electron beam treatments, oxidation treatments,
corona discharge treatments, chemical treatments, chromic acid
treatments, hot air treatments, ozone treatments, ultraviolet light
treatments, sand blast treatments, or solvent treatments.
28. The process of claim 27, wherein the film has been treated with
flame treatments, silanes, or poly(ally amine).
29. The process of claim 22, wherein the at least one film layer is
a solar control film layer.
30. The process of claim 29, wherein the solar control film is an
IR-reflective film or wherein the solar control film comprises:
indium tin oxide; antimony tin oxide; or lanthanum hexaboride.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority under 35 U.S.C. .sctn. 120
to U.S. Provisional Application No. 60/755,248, filed on Dec. 30,
2005, which is incorporated herein by reference in its
entirety.
FIELD OF THE INVENTION
[0002] This invention relates to laminates that have solar control
properties comprising at least one decorated polymer sheet layer
and a solar control film layer.
BACKGROUND OF THE INVENTION
[0003] Several patents and publications are cited in this
description in order to more fully describe the state of the art to
which this invention pertains. The entire disclosure of each of
these patents and publications is incorporated by reference
herein.
[0004] Glass laminates are widely used in the automotive and
construction industries. A prominent application is in safety glass
for automobile windshields. Safety glass is characterized by high
impact and penetration resistance and typically consists of a
laminate of two glass sheets bonded together with an interlayer of
a polymeric film or sheet. One or both of the glass sheets may be
replaced with optically clear rigid polymeric sheets, such as
sheets of polycarbonate materials. More complex safety glass
laminates include constructions composed of multiple layers of
glass and polymeric sheets that are bonded together with
interlayers of polymeric films or sheets.
[0005] A safety glass interlayer typically comprises a relatively
thick polymer film or sheet that exhibits toughness and bondability
and adheres to the glass in the event of a crack or impact. This
prevents scatter of glass shards. Generally, the polymeric
interlayer is characterized by a high degree of optical clarity and
low haze. Resistance to impact, penetration and ultraviolet light
is usually excellent. Other properties include long term thermal
stability, excellent adhesion to glass and other rigid polymeric
sheets, low ultraviolet light transmittance, low moisture
absorption, high moisture resistance and excellent long term
weatherability. Commonly used interlayer materials include
multicomponent compositions based on polyvinyl butyral (PVB),
polyurethane (PU), polyvinylchloride (PVC), linear low density
polyethylenes prepared in the presence of metallocene catalysts,
ethylene vinyl acetate (EVA), polymeric fatty acid polyamides,
polyester resins, such as polyethylene terephthalate, silicone
elastomers, epoxy resins, elastomeric polycarbonates, and the
like.
[0006] A recent trend has been the use of glass laminated products
known as architectural glass in the construction of homes and
office structures. Newer products include those specifically
designed to resist disasters. Some examples include hurricane
resistant glass, theft resistant glazings and blast resistant glass
laminated products. Certain of these products have strength
sufficient to resist intrusion even if the glass laminate has been
broken. Other products meet requirements for incorporation as
structural elements within buildings, for example as glass
staircases. Ethylene copolymer ionomer resins have found use as the
glass laminate interlayer material in certain of these products,
for example, hurricane resistant glass. Such ionomer resins offer
significantly higher strength than other common interlayer
materials, such as polyvinyl butyral and ethylene vinyl acetate
materials. For example, U.S. Pat. No. 6,432,522 discloses that
polyvinyl butyral resins have a modulus per ASTM Method D 638 of
less than 34.5 MPa (5000 psi), EVA materials have a modulus of
5.2-6.2 MPa (750-900 psi), while copolyethylene ionomer resins have
a modulus in the range of 235-552 MPa (34,000-80,000 psi). Various
ethylene copolymer ionomer resins are disclosed in U.S. Pat. Nos.
3,264,272; 3,322,734; 3,328,367; 3,338,739; 3,344,014; 3,355,319;
3,404,134; 3,471,460; 4,619,973; 4,732,944 and 4,906,703. Ethylene
copolymer ionomers have been used disclosed as interlayers in glass
or other transparent material laminates in U.S. Pat. Nos.
3,762,988; 4,663,228 4,668,574; 4,799,346; 5,002,820; 5,344,513;
5,759,698; 5,763,062, 5,895,721; 6,114,046; 6,187,448; 6,238,801;
6,265,054; 6,353,042; and 6,432,522; in U.S. Published Patent
Applications 2002/0155302 and 2003/0044579; in European Patent
Publication 483 087 A1; and in PCT Published Patent Applications WO
99/58334, WO 00/64670, and WO 2004/011755. U.S. Pat. No. 6,150,028,
discloses glass laminates which include ionomer resin interlayers
and glass with solar control characteristics. WO 01/60604 discloses
a laminated glazing which includes a transparent flexible plastic
that reflects infra-red radiation bonded between a ply of ionomer
resin and a ply of a polymer material.
[0007] It is known to include some form of image or decoration
within the laminated glass product. U.S. Pat. Nos. 3,973,058,
4,303,718, and 4,341,683 disclose a process for printing polyvinyl
butyral sheet material, used as a component in laminated safety
glass, with a solvent-based ink. Disclosures of tint bands are
found for example, in U.S. Pat. Nos. 3,008,858; 3,346,526;
3,441,361; and 3,450,552; and in Japanese Patent 2053298.
[0008] Disclosures of decorative window films may be found, for
example, in U.S. Pat. Nos. 5,049,433, 5,468,532, 5,505,801 and WO
83/03800 which disclose printed window films wherein the film may
be affixed to a glass window.
[0009] Decorative glass laminates have been produced through the
incorporation of decorated films. For example, U.S. Pat. No.
6,824,868, U.S. Patent Application Publication 2003/0203167 and
International Application WO 03/092999 disclose an interlayer for
laminated glass comprising a polymeric support film with at least
one printed color image, a polymeric film bonded to the support
film, an adhesive layer bonded to the polymeric support film
opposite of the interface between the polymeric support film and
the polymeric film and another adhesive layer bonded to the
polymeric film opposite of the interface between the polyethylene
terephthalate polymeric film and the support film. These references
teach that laminates of glass and decorated polyvinyl butyral
layers would not have the integrity to be used in many applications
due to low glass-to-interlayer adhesion. Other references
disclosing laminates having printed layers include U.S. Patent
Application Publications 2002/0119306, 2003/0091758, and European
Patent 0 160 510. European Patent 1 129 844 discloses a composite
stratified decorated glass and/or transparent plastic panel
characterized in that it comprises first and second glass or
transparent plastic panes and a film or sheet made from transparent
plastic that bears a decoration. The decorated transparent film or
sheet is placed between the two panes and is stably associated with
the panes by means of layers of suitable adhesives applied to the
panes by calendering or heat lamination. The adhesives include
polyurethanes and polyvinyl butyrals. Coating primers, such as
silane, polyurethane, epoxy, or acrylic primers may be used on the
transparent plastic film. Manufacture of such embedded decorated
film laminates is an inefficient method of production.
[0010] Decorative glass laminates derived from printed interlayers
are known in the art. For example, U.S. Pat. No. 4,968,553,
discloses an architectural glass laminate that includes an
interlayer of extruded polyurethane, heat-laminated between two
sheets of rigid material, wherein a non-solvent based ink
containing solid pigments is printed on the polyurethane interlayer
prior to lamination. For example, U.S. Pat. Nos. 4,173,672,
4,976,805, 5,364,479, 5,487,939 and 6,235,140 disclose a method for
producing a decorative intermediate film for use in laminated glass
sheet through a transfer print process. Ink jet printing a
temporary substrate and transfer printing the image onto a second
substrate is disclosed in WO 95/06564 and WO 2004/039607.
[0011] Decorative printed polyvinyl butyral sheets for glass
laminates are also known in the art. U.S. Pat. No. 5,914,178
discloses a laminated pane which comprises at least one visible
motif, the pane comprising at least one rigid sheet of one of a
glass material or a plastics material and at least one sheet of
flexible plastics material. The motif is at least partly formed of
at least one coating of organic ink epoxy layer. The reference
discloses that polyvinyl butyral and polyurethane plastics
materials may be utilized.
[0012] U.S. Patent Application Publication 2004/0187732 discloses
an ink jet ink set comprising non-aqueous, colored, pigmented inks,
at least one of which is a yellow ink comprising PY120 dispersed in
a non-aqueous vehicle. The use of this ink set in ink jet printing
of, for example, polyvinyl butyral substrates is disclosed, as is
the use of the printed substrate in preparation of laminated glass
articles. U.S. Patent Application Publication 2004/0234735 and WO
02/18154 disclose a method of producing image carrying laminated
material including the steps of forming an image on a first surface
of a sheet of interlayer using solvent based ink, paint or dye
systems, interposing the interlayer sheet between two sheets of
material and joining the two sheets of material to form the
laminate by activating the interlayer. WO 2004/011271 discloses a
process for ink-jet printing an image onto a rigid thermoplastic
interlayer comprising the steps of feeding a rigid interlayer sheet
through an ink jet printer and ink jet printing an image on the
sheet, wherein the interlayer has a Storage Young's Modulus of
50-1,000 MPa and wherein the rigid interlayer sheet has a finite
thickness of less than or equal to about 0.38 mm. WO 2004/018197
discloses a process for obtaining an image-bearing laminate having
a laminate adhesive strength of at least 1000 psi, which includes
ink jet printing a digital image onto a thermoplastic interlayer
selected from polyvinyl butyrals, polyurethanes, polyethylenes,
polypropylenes, polyesters, and EVA using a pigmented ink which
comprises at least one pigment selected from the group consisting
of PY120, PY155, PY128, PY180, PY95, PY93, PV19/PR202, PR122,
PR15:4, PB15:3, and PBI7.
[0013] Reduction of energy consumption within structures in which
glass is applied is very desirable and has led to development of
solar control glass structures. Typical solar control glass is
designed to eliminate or reduce energy from the near infrared
region of the electromagnetic spectrum. For example, the air
conditioning load may be reduced in buildings equipped with solar
control windows which block out a portion of the near infrared
region of the solar spectral range. Solar control glass laminates
may be obtained by modification of the glass itself, by
modification of polymeric interlayers used in laminated glass, and
by the addition of further solar control layers, such as in window
films. Metal oxide nanoparticles are often used in solar control
layers to absorb infrared light and convert energy to heat.
Materials having nominal particle sizes below about 50 nanometers
are used to preserve the clarity and transparency of the substrate.
Infrared-absorbing nanoparticles of commercial significance are
antimony tin oxide and indium tin oxide.
[0014] Antimony tin oxide nanoparticles and indium tin oxide
nanoparticles have been incorporated into polymeric interlayers of
glass laminates. Laminated glass which incorporates homogeneously
dispersed, functional, ultra-fine particles is disclosed in U.S.
Pat. Nos. 5,830,568; 6,315,848; 6,329,061; and 6,579,608. Laminated
glass that includes indium tin oxide particles dispersed within
plasticized polyvinyl butyral interlayers and certain types of
glass is disclosed in U.S. Pat. Nos. 6,506,487 and 6,686,032. U.S.
Pat. No. 6,632,274 discloses ultrafine particle dispersions in a
plasticizer and their use in polyvinyl butyral interlayers for
glass laminates. U.S. Pat. Nos. 6,620,477, 6,632,274 and 6,673,456
disclose laminated glass that contains indium tin oxide particles
dispersed within certain plasticized polyvinyl butyral interlayers.
U.S. Pat. No. 6,733,872 discloses sound proofed glass laminates
which include indium tin oxide particles dispersed within
plasticized polyvinyl butyral interlayers. European Patent
Application 1 227 070 A1 discloses an interlayer for laminated
glass comprising and adhesive resin.
[0015] Antimony tin oxide and indium tin oxide nanoparticles have
also been incorporated into coatings. Particle dispersions, coating
solutions, and coated substrates of these substances are disclosed
in U.S. Pat. Nos. 5,376,308; 5,504,133; 5,518,810; 5,654,090;
5,662,962; 5,742,118; 5,763,091; 5,772,924; 5,807,511; 5,830,568;
6,084,007; 6,191,884; 6,221,945; 6,261,684; 6,277,187; 6,315,848;
6,319,613; 6,329,061; 6,404,543; 6,416,818; 6,506,487; 6,528,156;
6,579,608; 6,620,477; 6,632,274; 6,663,950; 6,673,456; 6,686,032;
6,733,872; European Patent 947 566; and European Patent Application
1 154 000 A1. For example, U.S. Pat. No. 5,807,511 discloses a near
infrared screening filter composition which includes a metal oxide
or inorganic oxide powder and a dye. Japanese Patent Publication
2004124033 discloses a coating material which includes electrically
conductive transparent ultrafine particles and a polyester
substrate coated with the material that produces an
infrared-shielding film.
[0016] Film substrates coated with antimony tin oxide and indium
tin oxide materials have been disclosed as solar control window
coverings. U.S. Pat. No. 5,518,810, discloses the use of indium tin
oxide and antimony tin oxide particles in infrared ray cutoff
coatings. U.S. Pat. Nos. 6,191,884, 6,261,684 and 6,528,156
disclose coatings that contain indium tin oxide particles useful as
solar control window films. The films may be attached to windows
with a thin layer of contact adhesive.
[0017] Metal boride nanoparticles have also been utilized to absorb
infrared light and convert energy to heat. To preserve the clarity
and transparency of the substrate these materials have nominal
particle sizes below about 200 nanometers (nm). Metal boride
nanoparticles are reported to be more efficient than metal oxide
nanoparticles, resulting in the use of significantly reduced levels
of the former to attain equivalent performance. Infrared-absorbing
metal boride nanoparticles include lanthanum hexaboride. U.S. Pat.
No. 6,060,154 discloses a coating solution that contains lanthanum
hexaboride nanoparticles and solar control films produced
therefrom. U.S. Pat. Nos. 6,221,945 and 6,277,187 disclose a
coating solution containing lanthanum hexaboride nanoparticles and
solar control films produced by coating the nanoparticles onto a
substrate. U.S. Pat. No. 6,319,613 and European Patent 1 008 564
disclose coating solutions containing a combination of lanthanum
hexaboride and antimony tin oxide or indium tin oxide nanoparticles
for use in solar control window covering films. U.S. Pat. No.
6,663,950 discloses solar control window films comprising a
transparent polymeric film substrate having a UV-absorbing material
coated with a hardcoat layer. Polymeric dispersions of lanthanum
hexaboride nanoparticles are disclosed in U.S. Pat. No. 6,673,456.
WO 02/060988 discloses glass laminates prepared from polyvinyl
butyral resin containing lanthanum hexaboride or a mixture of
lanthanum hexaboride and indium tin oxide or antimony tin oxide.
Master batch compositions containing from 0.01 to about 20 parts by
weight of lanthanum hexaboride nanoparticles per 100 parts by
weight of a thermoplastic resin are disclosed in U.S. Published
Patent Application 2004/0028920.
[0018] A shortcoming of solar control laminates which incorporate
infrared absorptive materials is that a significant proportion of
the light absorbed serves to generate heat. This is especially true
when the laminates are used in structures such as parking garages.
In such situations, reflective solar control laminates are
desirable because they do not increase in temperature by absorbing
solar energy.
[0019] Metallized substrate films have been used in solar control
laminates. These include polyester films which have electrically
conductive metal layers, such as aluminum or silver metal,
typically applied through a vacuum deposition or a sputtering
process. These structures and their use in glass laminates is
disclosed in U.S. Pat. Nos. 3,718,535; 3,816,201; 3,962,488;
4,017,661; 4,166,876; 4,226,910; 4,234,654; 4,368,945; 4,386,130;
4,450,201; 4,465,736; 4,782,216; 4,786,783; 4,799,745; 4,973,511;
4,976,503; 5,024,895; 5,069,734; 5,071,206; 5,073,450; 5,091,258;
5,189,551; 5,264,286; 5,306,547; 5,932,329; 6,391,400 and
6,455,141. U.S. Pat. Nos. 4,782,216 and 4,786,783 disclose a
transparent, laminated window with near IR rejection that includes
two transparent conductive metal layers. U.S. Pat. No. 4,973,511
discloses a laminated solar window construction which includes a
PET sheet with a multilayer solar coating. U.S. Pat. No. 4,976,503
discloses an optical element that includes light-reflecting metal
layers. Reflecting interference films are disclosed in U.S. Pat.
No. 5,071,206. U.S. Pat. No. 5,091,258 discloses a laminate that
incorporates an infra-red radiation reflecting interlayer. A
laminated glass pane having a transparent support film of
tear-resistant polymer provided with an IR-reflecting coating and
two adhesive layers is disclosed in U.S. Pat. No. 5,932,329. U.S.
Pat. No. 6,204,480 discloses thin film conductive sheets for
windows while U.S. Pat. No. 6,391,400 discloses dielectric layer
interference effect thermal control glazings for windows. U.S. Pat.
No. 6,455,141 discloses laminated glass that incorporates an
interlayer having an energy-reflective coating. European Patent 0
418 123 discloses laminated glass with an interlayer comprising a
copolymer of vinyl chloride and glycidyl methacrylate.
[0020] One shortcoming of decorative laminates of the prior art is
the low level of adhesion between the printed surface and the other
laminate layers. The colorant has been considered to be the primary
cause of this phenomenon. While strides have been made within the
art to overcome this problem, greater laminate adhesion would be
desirable for a wide array of end uses. The present invention
addresses this issue and provides decorated laminates with
excellent laminate adhesion, superior penetration resistance and
solar control properties.
SUMMARY OF THE INVENTION
[0021] The present invention is directed to a laminate comprising
at least one layer of a decorated polymer sheet and a layer of a
film, preferably a solar control film. In particular, the present
invention relates to a laminate comprising at least one layer of a
polymer sheet having upper and lower surfaces and having a
thickness of at least about 0.25 mm. The polymer sheet comprises a
polymer composition that has a modulus of between about 20,000 psi
(138 MPa) and about 100,000 psi (690 MPa), as determined according
to ASTM D 638-03. At least one of the surfaces of the polymer sheet
has an image and preferably an adhesive composition disposed
thereon, and at least a portion of the adhesive composition is in
contact with said image. The laminate also comprises at least one
other film layer.
[0022] The present invention is also directed to a process for
preparing a laminate comprising the steps of: (1) forming an
image-bearing surface on a polymer sheet by applying an image to at
least one surface of a polymer sheet having upper and lower
surfaces, said polymer sheet having a thickness of at least about
0.25 mm, said polymer sheet comprising a polymer composition having
a modulus of between about 20,000 psi (138 MPa) and about 100,000
psi (690 MPa), as determined according to ASTM D 638-03; (2)
optionally applying an adhesive composition to at least a portion
of said one or more image-bearing surfaces; and (3) laminating at
least one of the image-bearing surfaces to at least one film
layer.
[0023] The present invention is also directed to a process for
preparing a decorative solar control laminate comprising the steps
of: (1) forming an image-bearing surface on a polymer sheet by
applying an image to at least one surface of a polymer sheet having
upper and lower surfaces, said polymer sheet having a thickness of
at least about 0.25 mm, said polymer sheet comprising a polymer
composition having a modulus of between about 20,000 psi (138 MPa)
and about 100,000 psi (690 MPa), as determined according to ASTM D
638-03; (2) optionally applying an adhesive composition to at least
a portion of said image-bearing surface; and (3) laminating the
image-bearing surface to at least one solar control film layer.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The definitions herein apply to the terms as used throughout
this specification, unless otherwise limited in specific
instances.
[0025] The term "modulus" as used herein, refers to a modulus that
is measured in accord with ASTM Standard D 638-03.
[0026] The term "(meth)acrylic acid" as used herein refers to
acrylic acid or methacrylic acid, or to a mixture of acrylic acid
and methacrylic acid. The term "(meth)acrylate" as used herein
refers to a salt or ester of acrylic acid, methacrylic acid, or of
a mixture of acrylic acid and methacrylic acid.
[0027] The terms "finite amount" and "finite value", as used
herein, refer to an amount or value that is greater than zero.
[0028] As used herein, the term "about" means that amounts, sizes,
formulations, parameters, and other quantities and characteristics
are not and need not be exact, but may be approximate and/or larger
or smaller, as desired, reflecting tolerances, conversion factors,
rounding off, measurement error and other factors that will be
apparent to those of skill in the art. In general, an amount, size,
formulation, parameter or other quantity or characteristic is
"about" or "approximate" whether or not expressly stated to be
such.
[0029] The term "or", when used alone herein, is inclusive; more
specifically, the phrase "A or B" means "A, B, or both A and B".
Exclusive "or" is designated herein by terms such as "either A or
B" and "one of A or B", for example.
[0030] When materials, methods, or machinery are described herein
with the term "known to those of skill in the art", or a synonymous
word or phrase, the term signifies that materials, methods, and
machinery that are conventional at the time of filing the present
application are encompassed by this description. Also encompassed
are materials, methods, and machinery that are not presently
conventional, but that will have become recognized in the art as
suitable for a similar purpose.
[0031] All percentages, parts, ratios, and the like set forth
herein are by weight, unless otherwise limited in specific
instances.
[0032] In addition, the ranges set forth herein include their
endpoints unless expressly stated otherwise. Further, when an
amount, concentration, or other value or parameter is given as a
range, one or more preferred ranges or a list of upper preferable
values and lower preferable values, this is to be understood as
specifically disclosing all ranges formed from any pair of any
upper range limit or preferred value and any lower range limit or
preferred value, regardless of whether such pairs are separately
disclosed.
[0033] The present invention is directed to certain laminates
having at least one layer that is a decorated polymeric sheet. As
used herein, the term "decorated polymeric sheet" means a polymer
sheet that has an image disposed thereon, also referred to herein
as an image-bearing polymer sheet. The decorated sheet comprises a
polymer composition that has a modulus of between about 20,000 psi
(138 MPa) and about 100,000 psi (690 MPa), as determined by ASTM
Method D-638 to provide high laminate impact resistance and
penetration resistance. Preferably, the decorated sheet comprises a
polymer composition having a modulus of between about 25,000 psi
(173 MPa), and about 90,000 psi (621 MPa), to provide even higher
laminate impact resistance and penetration resistance. More
preferably, the decorated sheet comprises a polymer composition
having a modulus of between about 30,000 psi (207 MPa), and about
80,000 psi (552 MPa), to provide yet even higher laminate impact
resistance and penetration resistance. Preferably, the polymer
sheet consists of or consists essentially of the polymer
composition.
[0034] Preferred polymer compositions comprise one or more of an
ethylene acid copolymer, a polyvinyl chloride and a polyurethane.
The ethylene acid copolymers preferably incorporate from between
about 0.1 weight percent to about 30 weight percent or, still more
preferably, from about 1.0 weight percent to about 25 weight
percent of copolymerized residues having acid functionality, based
on the total weight of the copolymer. Ethylene copolymers and
ethylene copolymer ionomers that incorporate from about 15 weight
percent to about 25 weight percent of copolymerized residues having
acid functionality, based on the total weight of the polymer, are
particularly preferred, because of their especially enhanced
adhesion to glass.
[0035] The acid functionality is generally derived from
copolymerized residues of one or more unsaturated carboxylic acids
or unsaturated carboxylic acid anhydrides. Preferably, the acid
functionality results from copolymerized units of carboxylic acids
and carboxylic acid anhydrides including acrylic acid, methacrylic
acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid,
monomethyl maleic acid, and mixtures thereof. Ethylene acid
copolymers comprising copolymerized units of acrylic acid and
methacrylic acid are especially preferred.
[0036] The ethylene acid copolymers may optionally contain
copolymerized residues of one or more other unsaturated comonomers,
such as acrylate esters. Preferably, the unsaturated comonomers are
selected from the group consisting of methyl acrylate, methyl
methacrylate, butyl acrylate, butyl methacrylate, glycidyl
methacrylate, vinyl acetate, and mixtures thereof. Preferably, the
ethylene acid copolymers incorporate a finite amount up to about 50
weight percent of the optional unsaturated comonomer or comonomers,
based on the total weight of the ethylene copolymer. More
preferably, the ethylene copolymers and ethylene copolymer ionomers
a finite amount up to about 25 weight percent of the optional
unsaturated comonomer, based on the total weight of the
composition. Most preferably, the ethylene copolymers and ethylene
copolymer ionomers incorporate a finite amount up to about 10
weight percent of the other unsaturated comonomer, based on the
total weight of the composition. The ethylene copolymers may be
prepared by copolymerization as disclosed, for example, in U.S.
Pat. Nos. 3,404,134; 5,028,674; 6,500,888 and 6,518,365.
[0037] The ethylene acid copolymers may optionally be neutralized
to form the corresponding ionomers. Ionomers of ethylene acid
copolymers are also suitable for use in the polymer composition,
providing that the modulus of the polymer composition remains with
in the suitable range. Neutralization levels may be low, i.e.,
below 1 percent, or high, including 100 percent neutralization,
based on total carboxylic acid content. Neutralization will take
place using metallic ions. The metallic ions may be monovalent or
multivalent, including divalent and trivalent metallic ions.
Mixtures of such ion classes may also be used. Preferable
monovalent metallic ions include sodium, potassium, lithium,
silver, mercury, copper, and the like and mixtures thereof.
Preferable divalent metallic ions include beryllium, magnesium,
calcium, strontium, barium, copper, cadmium, mercury, tin, lead,
iron, cobalt, nickel, zinc, and the like and mixtures thereof.
Preferable trivalent metallic ions include of aluminum, scandium,
iron, yttrium, and the like and mixtures thereof. Other useful
multivalent metallic ions include titanium, zirconium, hafnium,
vanadium, tantalum, tungsten, chromium, cerium, iron, and the like
and mixtures thereof. Preferably, when the metallic ion is
multivalent, complexing agents that include stearates, oleates,
salicylates, and phenolates are used. Such compositions are
disclosed, for example in U.S. Pat. No. 3,404,134. Sodium, lithium,
magnesium, zinc, aluminum, and mixtures thereof are especially
useful metallic ions. Most preferably, the metallic ion is selected
from the group consisting of sodium, zinc, and mixtures thereof.
Sodium is most preferred due to high optical clarity of sheets
comprising ethylene copolymer sodium ionomers. Zinc ionomers
imparts high moisture resistance and is an especially useful
metallic ion. Preferably, the ethylene acid copolymer ionomers will
be neutralized from about 10 to about 90 percent with metallic ions
based on the total carboxylic acid content. More preferably, the
ethylene acid copolymer ionomers will be neutralized from about 20
to 80 percent with metallic ions based on the total carboxylic acid
content. Processes for neutralization of ionomers are well known in
the art, for example as disclosed in U.S. Pat. No. 3,404,134.
[0038] The ethylene copolymer compositions that comprise the
polymeric sheet may optionally incorporate additives which act to
reduce the melt flow of the resin. As will be familiar to those
skilled in the art, such additives may be used in amounts that do
not interfere with or prevent production of thermoset films and
sheets. The use of such additives enhances the upper enduse
temperature of the sheet and laminates made therefrom. Typically,
the enduse temperature will be enhanced by 20.degree. to 70.degree.
C. In addition, laminates produced from sheets that incorporate
such additives will be more fire resistant than laminates wherein
the sheets of the layers do not incorporate additives. By reducing
the melt flow of the ethylene copolymer sheet, it will have a
reduced tendency to melt and flow out of a laminate and, in turn,
serve as additional fuel for a fire. Specific examples of melt flow
reducing additives include organic peroxides, such as
2,5-dimethylhexane-2,5-dihydroperoxide,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3, di-t-butyl peroxide,
t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
dicumyl peroxide, alpha,alpha'-bis(t-butyl-peroxyisopropyl)benzene,
n-butyl-4,4-bis(t-butylperoxy)valerate,
2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butyl-peroxy)cyclohexane,
1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, t-butyl
peroxybenzoate, benzoyl peroxide, and the like and mixtures and
combinations thereof. Organic peroxides that decompose at
temperatures of about 100.degree. C. or higher are preferred. More
preferably, the organic peroxides will have a decomposition
temperature which affords a half life of 10 hours at about
70.degree. C. or higher to provide improved stability for blending
operations. Typically, the organic peroxides will be added at a
level of up to about 10 weight percent based on the total weight of
the ethylene copolymer composition. If desired, initiators, such as
dibutyltin dilaurate, may be used. Typically, initiators are added
at a level of up to about 0.05 weight percent based on the total
weight of the ethylene copolymer composition. If desired,
inhibitors, such as hydroquinone, hydroquinone monomethyl ether,
p-benzoquinone, and methylhydroquinone, may be added for the
purpose of enhancing control to the reaction and stability.
Typically, the inhibitors would be added at a level of less than
about 5 weight percent based on the total weight of the ethylene
copolymer composition.
[0039] Specific preferred examples of the polymeric sheet materials
include, for example, copolymers of ethylene and methacrylic acid
and ionomers thereof, copolymers of ethylene and acrylic acid and
ionomers thereof, lotek.RTM. ionomer resins available from the
Exxon Corporation, IMAC.RTM. ionomer resins available from the
Chevron Corporation, certain polyvinyl chloride resins, certain
impact-resistant, rigid polyurethane materials, for example,
available from The Dow Chemical Company.
[0040] It is understood that the polymer composition may
incorporate various additives known within the art. Such additives
may include, for example, plasticizers, processing aids, flow
enhancing additives, lubricants, colorants, pigments, dyes, flame
retardants, impact modifiers, nucleating agents to increase
crystallinity, antiblocking agents such as silica, thermal
stabilizers, slip agents, UV absorbers, UV stabilizers,
dispersants, surfactants, chelating agents, coupling agents,
adhesives, primers and the like. The amount of a particular
additive used will depend upon the type of additive and the
particulars of the polymer composition. For example, a UV
stabilizer level could be used at levels as low as 0.1 weight
percent, while a plasticizer might be used at a level of more than
30 weight percent. Methods for selecting and optimizing the
particular levels and types of additives for the polymers
comprising the sheet material are known to those skilled in the
art.
[0041] Colorants may be added to the polymer composition to provide
pigmentation or to control the amount of transmitted solar light.
Typical colorants may include any that are known in the art, for
example a bluing agent to reduce yellowing.
[0042] The polymers comprising the sheet may be formulated to
incorporate infrared absorbents, such as inorganic infrared
absorbents, for example indium tin oxide (ITO) nanoparticles and
antimony tin oxide (ATO) nanoparticles, and organic infrared
absorbents, for example polymethine dyes, amminium dyes, imminium
dyes, dithiolene-type dyes and phthalocyanine-type dyes and
pigments. Methods for selecting and optimizing the particular
levels and types of additives for the polymers comprising the sheet
material are known to those skilled in the art.
[0043] Any known thermal stabilizer or mixture of thermal
stabilizers will find utility within the polymer composition.
Useful thermal stabilizers include phenolic antioxidants, alkylated
monophenols, alkylthiomethylphenols, hydroquinones, alkylated
hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers,
alkylidenebisphenols, O-, N- and S-benzyl compounds,
hydroxybenzylated malonates, aromatic hydroxybenzyl compounds,
triazine compounds, aminic antioxidants, aryl amines, diaryl
amines, polyaryl amines, acylaminophenols, oxamides, metal
deactivators, phosphites, phosphonites, benzylphosphonates,
ascorbic acid, compounds which destroy peroxide, hydroxylamines,
nitrones, thiosynergists, benzofuranones, indolinones, and the
like. Generally, when used, thermal stabilizers will be present in
the polymer composition in an amount of 0.001 to 10 weight percent,
based on the total weight of the polymer composition. Preferably,
0.001 to about 5.0 weight percent thermal stabilizers, based on the
total weight of the composition, will be used. More preferably 0.05
to about 1.0 weight percent thermal stabilizers, based on the total
weight of the polymer composition, will be used.
[0044] The polymer composition may contain a UV absorber or a
mixture of UV absorbers. Preferable general classes of UV absorbers
include benzotriazoles, hydroxybenzophenones, hydroxyphenyl
triazines, esters of substituted and unsubstituted benzoic acids,
and the like and mixtures thereof. Any UV absorber known in the art
will find utility within the polymer composition, which preferably
incorporate from about 0.001 to about 10.0 weight percent UV
absorbers, based on the total weight of the composition, more
preferably 0.001 to 5.0 weight percent, based on the total weight
of the polymer composition and most preferably, 0.05 to 1.0 weight
percent, based on the total weight of the composition.
[0045] The polymer composition may also incorporate an effective
amount of a hindered amine light stabilizers (HALS). Generally,
HALS are understood to be secondary, tertiary, acetylated,
N-hydrocarbyloxy substituted, hydroxy substituted, N-hydrocarbyloxy
substituted or other substituted cyclic amines which further have
some degree of steric hindrance, generally derived from aliphatic
substitution on the carbon atoms adjacent to the amine function.
When used, HALS are preferably present in amounts of from 0.001 to
10.0 weight percent, based on the total weight of the polymer
composition, more preferably from 0.05 to 5.0 weight percent, based
on the total weight of the polymer composition, most preferably
from 0.05 to 1.0 weight percent based on the total weight of the
polymer composition.
[0046] The image-bearing polymeric sheet useful in the present
invention has a thickness of greater than about 0.25 mm (10 mils)
or greater. This thickness provides enhanced penetration strength
of laminates that incorporate the sheet as a layer. Preferably, the
decorated polymeric sheet has a thickness of at least about 0.38 mm
(15 mils), more preferably at least about 0.75 mm (30 mils), which
thickness provides a further enhancement of penetration strength.
Even more preferably, the polymeric sheets of the invention have a
thickness of about 1.25 mm (50 mils) or greater to provide even
further enhanced penetration strength. The enhanced penetration
strength satisfies many requirements mandated for hurricane and
threat resistance. Certain uses require laminate interlayers to be
even thicker. Interlayers thicker than 60 mils (1.50 mm), 90 mils
(2.25 mm) and even thicker than 120 mils (3.00 mm) have been used
for certain applications. Preferably, the decorated polymeric
sheets incorporate rough surfaces to facilitate de-airing during
lamination processes.
[0047] The polymeric sheet may be formed by any of the processes
known in the art, such as extrusion, calendering, solution casting
or injection molding. Selection of the method and parameters will
depend upon the viscosity characteristics of the polymeric material
used and the desired thickness of the sheet. Preferably the
polymeric sheet is formed by extrusion, especially for manufacture
of "endless" products, such as films and sheets. In extrusion
processes, which are typically conducted at melt temperatures of
50.degree. C. to about 300.degree. C., the polymeric material is
fluidized and homogenized. Preferably, the melt processing
temperature is from about 100.degree. C. to about 250.degree. C.
Recycled polymeric compositions may be used along with the virgin
polymeric compositions. The polymer composition is forced through a
suitably shaped die to produce the desired cross-sectional sheet
shape. Sheets of different widths and thickness may be produced
through use of appropriate dies, for example slot dies or circular
dies. Using extruders known in the art a sheet can be produced by
extruding a layer of polymer over chilled rolls and then further
drawing down the sheet to the desired size by means of tension
rolls.
[0048] A sheeting calender is employed for manufacture of large
quantities of sheets. If the sheet is required to have a textured
surface, an appropriate embossing pattern may be applied through
use of an embossing roller or an embossing calender.
[0049] The polymeric sheet may have a smooth surface, but
preferably it will have a roughened surface to permit most of the
air to be removed between layers during lamination processes.
Surface roughening may be accomplished, for example, by
mechanically embossing the sheet after extrusion or by melt
fracture during extrusion of the sheet and the like. This rough
surface is only temporary and particularly functions to facilitate
deairing during laminating after which it is melted smooth as a
result of the elevated temperature and pressure associated with
autoclaving and other lamination processes. Surface patterns on the
polymeric sheet are important parameters in facilitating deairing
during the lamination process. An acceptable range of R.sub.z for
the stiff, rigid polymeric sheet is from about 5 to about 15
micrometers.
[0050] The properties exhibited by the polymer sheet will depend on
many factors including the polymer composition, the method of
forming the polymer, the method of forming the sheet, and whether
the sheet was treated by stretching or biaxially oriented. These
factors affect many properties such as shrinkage, tensile strength,
elongation at break, impact strength, dielectric strength and
constant, tensile modulus, chemical resistance, melting point, heat
deflection temperature, and the like.
[0051] The polymer sheets of the present invention may be further
modified to provide valuable attributes to the sheets and to the
laminates produced therefrom. For example, the sheets of the
present invention may be treated by radiation, for example,
electron beam treatment of the films and sheets. Electron beam
treatment of the sheets of the present invention with an intensity
in the range of about 2 MRd to about 20 MRd will provide an
increase in the softening point of the sheet (Vicat Softening
Point) of about 20.degree. C. to about 50.degree. C. Preferably,
the radiation intensity is from about 2.5 MRd to about 15 MRd.
[0052] The sheet will have at least one image disposed on at least
one surface, i.e. on the upper (or the surface closest to the
exterior surface of a glazing laminate) or lower (or the surface
closest to the interior surface of a glazing laminate) surface of
the sheet. Images may also be disposed on both the upper and lower
surfaces of the sheet. The images may completely cover the sheet or
they may be disposed on a small portion of the sheet. Depending on
the method of application of the image, the percent coverage of the
sheet may be above 100 percent. That is, the coverage of the image
is determined by the number of inks utilized within a particular
ink set. This can include application by multistrikes on the same
area. Generally this provides for up to 100 percent coverage on the
polymeric sheet for each ink used within a certain ink set. Thus,
for example, if application of the image takes place using an
inkjet printer and the ink set includes three inks, up to 300
percent coverage is possible. The term "percent coverage", as used
herein, is not to be confused with the percentage of the surface
that is occupied by the image. For example, an image may occupy
essentially 100% of the sheet's surface, but the percent coverage
may be 10%, as for a translucent display or the like.
Alternatively, an image may occupy 10% of the sheet's surface, but
the percent coverage of the image may be 300%, as for a small
design with saturated colors. Preferably, the image is disposed on
at least ten percent of the surface of at least one of said
surfaces of said sheet. Also preferably, the image has a percent
coverage of at least ten percent. One of ordinary skill in the art
of inkjet printing will know how to determine the appropriate
coverage for a given decorated sheet.
[0053] The image may be applied to the sheet by any known art
method. Such methods may include, for example; air-knife, printing,
painting, Dahlgren, flexography, gravure, spraying, thermal
transfer printing, silk screen, thermal transfer, inkjet printing
or other art processes. The image may be, for example, a symbol,
geometric pattern, photograph, alphanumeric character and the like
or a layer of ink. In addition, combinations of such images may be
utilized.
[0054] Preferably, the image is applied to the sheet by a digital
printing process. A major advantage of digital printing is the
minimal setup times required to produce an image. Such processes
provide speed and flexibility. Examples of digital printing
processes include, for example, thermal transfer printing and
inkjet printing.
[0055] Thermal transfer printing, which is a dry-imaging process
that involves the use of a printhead containing many resistive
heating elements that selectively transfer solid ink from a coated
ribbon to a substrate, is often used in applications such as
printing bar codes onto labels and tags.
[0056] More preferably, the image is applied to the polymer sheet
through an ink jet printing process. Ink jet printing is used in
applications including desktop publishing and digital photography.
It is also suitable for printing on textiles and fabrics. Ink jet
printing is typically a wet-imaging, non-contact process in which a
vehicle or carrier fluid is energized to "jet" ink components from
a printhead over a small distance onto a substrate. Ink jet
technologies include continuous and drop-on-demand types, with the
drop-on-demand printing being the most common. Ink jet printheads
generally fall within two broad categories: thermal printheads,
mainly used with aqueous inks, and piezo-electric printheads,
mainly used with solvent inks. In one particularly useful
embodiment, the image is printed onto the polymer sheet using a
piezo-electric drop-on-demand digital printing process.
[0057] The type of ink used in ink jet application of the image to
the polymer sheet is not critical. Any of the common ink jet type
inks are suitable. The ink may be solvent based, often referred to
in the art as a "non-aqueous vehicle", which term refers to an ink
vehicle that comprises one or more solvents that are non-aqueous or
substantially free of water. Solvent based inks may also comprise a
colorant that is dissolved, e.g., a dye. Solvents may be polar
and/or nonpolar. Examples of polar solvents include, for example,
alcohols, esters, ketones and ethers, particularly mono- and
di-alkyl ethers of glycols and polyglycols such as monomethyl
ethers of mono-, di- and tri-propylene glycols and the mono-n-butyl
ethers of ethylene, diethylene, and triethylene glycols. Useful,
but less preferred polar solvents include, for example, methyl
isobutyl ketone, methyl ethyl ketone, butyrolactone and
cyclohexanone. Examples of nonpolar solvents include, for example,
aliphatic and aromatic hydrocarbons having at least six carbon
atoms and mixtures of such materials, including refinery
distillation products and byproducts. Adventitious water may be
carried into the ink formulation, generally at levels of no more
than about 24 percent by weight. By definition, the term
"non-aqueous ink" as used herein refers to an ink having no more
than about 11 weight percent, and preferably no more than about 5
weight percent, of water based on the total weight of the
non-aqueous vehicle.
[0058] The ink may also be aqueous or water based. Typically,
aqueous inks comprise a colorant that is dispersed rather than
completely dissolved, e.g., a pigment. Combinations of solvent and
water based inks are also useful.
[0059] In addition to the colorant, an ink jet ink formulation may
contain humectants, surfactants, biocides, and penetrants and other
ingredients known to those skilled in the art.
[0060] The amount of the vehicle in the ink is typically in the
range of about 70 weight percent to about 99.8 weight percent, and
preferably about 80 weight percent to about 99.8 weight percent,
based on the total weight of the ink.
[0061] Preferably, the ink comprises pigments. Pigment colorants
have enhanced color fastness compared to dyes. They also exhibit
excellent thermal stability, edge definition, and low diffusivity
on the printed substrate. Preferably, however, solvent based ink is
used as the ink jet ink due to the difference in dispersion
properties. Standards of dispersion quality are high in ink jet
printing processes. While pigments may be "well dispersed" for
certain applications, dispersion may be inadequate for ink jet
applications.
[0062] Preferably, the ink jet printing process allows for the use
of flat sheet stock which is not stored or fed from rolls of sheet.
The polymeric sheet of the present invention has a high modulus and
tends to be too stiff to be rolled. This is especially true for
polymeric sheet thicknesses of 0.75 mm (30 mils) or greater. The
polymer sheet is preferably thick to provide penetration strength
of high strength laminates that may be produced using the sheet as
one or more layers of a laminate. It is further preferable that the
polymeric sheet be thick to reduce the number of layers when the
polymeric sheet is used in certain laminate applications. The
greater thickness of the polymeric sheet further allows for a
simplification of the printing process by significantly reducing or
eliminating the need for backing layers or sacrificial webs to
provide dimensional stability to the polymeric sheet during the
printing process, while maintaining high quality images.
[0063] Ink jet printing processes which allow the use of flat sheet
stock are well known. Generally, flat bed ink jet printers are
utilized in such processes. Typically, the printing process is one
of two general types. In one process, the flat sheet stock is moved
across the printhead(s) during the printing process, generally
through the use of rollers. In an alternative process, the
printhead(s) move across the sheet stock immobilized in the flat
bed. Examples of commercially-available, wide-format inkjet
printers include the NUR Tempo.RTM. Modular Flatbed Inkjet Presses
manufactured by NUR Microprinters of Monnachie, N.J. These are
piezo drop-on-demand printers which may include up to 18 piezo
drop-on-demand print heads.
[0064] Preferably, the ink set comprises at least three different,
non-aqueous, colored pigmented inks (CMY), at least one of which is
a magenta ink, at least one of which is a cyan ink, and at least
one of which is a yellow ink dispersed in a non-aqueous vehicle.
The yellow pigment preferably is chosen from the group consisting
of Color Index PY120, PY155, PY128, PY180, PY95, PY93 and mixtures
thereof. More preferably, the yellow pigment is Color Index PY120.
A commercial example is PV Fast Yellow H2G (Clariant). This pigment
has the advantageous color properties of favorable hue angle, good
chroma, and light fastness and further disperses well in
non-aqueous vehicle. Most preferably, the magenta ink comprises a
complex of PV19 and PR202 (also referred to as PV19/PR202)
dispersed in a non-aqueous vehicle. A commercial example is
Cinquasia Magenta RT-255-D (Ciba Specialty Chemicals Corporation).
The pigment particles can comprise an intimate complex of the PV19
and PR202 species, not simply a physical mixture of the individual
PV19 and PR202 crystals. This pigment has the advantageous color
properties of quinacridone pigments such as PR122 with favorable
hue angle, good chroma, and light fastness and further disperses
well in non-aqueous vehicle. In contrast, PR122 pigment does not
disperse well under similar conditions. Also preferred is a cyan
ink comprising PB 15:3 and/or PB 15:4 dispersed in a non-aqueous
vehicle. Other preferable pigments include, for example, PR122 and
PBI7. The ink set will commonly additionally include a non-aqueous,
pigmented black ink, comprising a carbon black pigment. Preferably,
the ink set comprises at least four inks (CMYK). The ink set may
comprise a greater number of inks. For example, mixtures of six
inks and eight inks are common.
[0065] Additional pigments for ink jet applications are generally
well known. A representative selection of such pigments may be
found, for example, in U.S. Pat. Nos. 5,026,427; 5,086,698;
5,141,556; 5,169,436 and 6,160,370. The exact choice of pigment
will depend upon color reproduction and print quality requirements
of the application.
[0066] Generally, pigments are stabilized in a dispersion by
employing dispersing agents, such as polymeric dispersants or
surfactants. "Self-dispersible" or "self-dispersing" pigments
("SDP(s)") have been developed that are dispersible in a vehicle
without added dispersants. The dispersant can be a random or
structured polymeric dispersant. Random polymers include acrylic
polymers and styrene-acrylic polymers. Structured dispersants
include AB, BAB and ABC block copolymers, branched polymers and
graft polymers. Useful structured polymers are disclosed in, for
example, U.S. Pat. Nos. 5,085,698 and 5,231,131 and in European
Patent Application 0556649. Examples of typical dispersants for
non-aqueous pigment dispersions include those sold under the trade
names Disperbyk (BYK-Chemie, USA), Solsperse (Avecia) and EFKA
(EFKA Chemicals) polymeric dispersants. SDPs for non-aqueous inks
include, for example, those described in U.S. Pat. Nos. 5,698,016;
U.S. Published Patent Applications 2001003263; 2001004871 and
20020056403 and PCT Publication WO 01/94476.
[0067] It is desirable to use small pigment particles for maximum
color strength and good jetting of ink. The particle size is
generally in the range of from about 0.005 microns to about 15
microns, preferably in the range of about 0.01 to about 0.3 micron.
The levels of pigment employed in the inks is typically in the
range of from about 0.01 to about 10 weight percent, based on the
total weight of the ink.
[0068] The solvent or aqueous inks may optionally contain one or
more other ingredients such as surfactants, binders, bactericides,
fungicides, algicides, sequestering agents, buffering agents,
corrosion inhibitors, light stabilizers, anti-curl agents,
thickeners, and/or other additives and adjuvants well know within
the relevant art. The amount of each ingredient is typically below
about 15 weight percent and more typically below about 10 weight
percent, based on the total weight of the ink. Useful surfactants
include ethoxylated acetylene diols (e.g. Surfynols.RTM. series
from Air Products), ethoxylated primary alcohols (e.g. Neodol.RTM.
series from Shell) and secondary alcohols (e.g. Terigitol.RTM.
series from Union Carbide), sulfosuccinates (e.g. Aerosol.RTM.
series from Cytec), organosilicones (e.g. Silwet.RTM. series from
Witco) and fluoro surfactants (e.g. Zonyl.RTM. series from DuPont).
Surfactants are typically utilized in amounts of about 0.01 to
about 5 weight percent, preferably in amounts of about 0.2 to about
2 weight percent, based on the total weight of the ink.
[0069] The ink vehicle may also comprise a binder. Useful types of
binders are soluble or dispersed polymer(s) added to the ink to
improve the adhesion of a pigment. Examples include polyesters,
polystyrene/acrylates, sulfonated polyesters, polyurethanes,
polyimides, polyvinyl pyrrolidone/vinyl acetate (PVPNA), polyvinyl
pyrrolidone (PVP) and mixtures thereof. Binders are generally used
at levels of at least about 0.3 weight percent, preferably at least
about 0.6 weight percent, based on the total weight of the ink.
Upper limits are dictated by ink viscosity or other physical
limitations, or by desired properties, such as ink drying time or a
desired level of durability in the image.
[0070] Non-aqueous vehicles may also be comprised entirely or in
part of polymerizable solvents, such as solvents which cure upon
application of actinic radiation (actinic radiation curable) or UV
light (UV curable). Specific examples of the radically
polymerizable monomers and oligomers which may serve as components
within such reactive solvent systems include, for example, vinyl
monomers(meth)acrylate esters, styrene, vinyltoluene,
chlorostyrene, vinyl acetate, allyl alcohol, maleic acid, maleic
anhydride, maleimide, N-methylmaleimide(meth)acrylic acid, itaconic
acid, ethylene oxide-modified bisphenol A,
mono(2-(meth)acryloyloxyethyl) acid phosphate,
phosphazene(meth)acrylate compounds, urethane (meth)acrylate
compounds, prepolymers having at least one (meth)acryloyl group,
polyester(meth)acrylates, polyurethane (meth)acrylates,
epoxy(meth)acrylates, polyether(meth)acrylates,
oligo(meth)acrylates, alkyd(meth)acrylates, polyol(meth)acrylates,
silicone(meth)acrylates, tris[(meth)acryloyloxyethyl] isocyanurate,
saturated or unsaturated mixed polyester compounds of (meth)acrylic
acid having one, two or more (meth)acryloyloxy groups in a molecule
and the like and mixtures thereof.
[0071] Actinic radiation-curable compositions generally contain a
minor amount of a photoinitiator. Specific examples include
1-hydroxycyclohexyl phenyl ketone, benzophenone,
benzyldimethylketal, benzoin methyl ether, benzoin ethyl ether,
p-chlorobenzophenone, 4-benzoyl-4-methyldiphenyl sulfide,
2-benzyl-2-dimethylamino-1-(4-morpholino-phenyl)butanone-1,2-met-
hyl-1-4-(methylthio)phenyl-2-morpholinopropanone-1, diethoxy
acetophenone, and others. Photo-cationic polymerization initiators
may also be employed. One or more photoinitiators may be added at a
total level of from about 0.1 weight percent to about 20 weight
percent based on the weight of total ink composition. Preferably
from about 0.1 weight percent to about 15.0 weight percent of the
photoinitiator is used, based on the total weight of the ink
composition.
[0072] Alternatively, the image may be formed from a
photo-cationic-curable material. Generally,
photo-cationically-curable materials incorporate epoxide and/or
vinyl ether materials. The compositions may optionally include
reactive diluents and solvents. Specific examples of preferable
optional reactive diluents and solvents include epoxide-containing
and vinyl ether-containing materials, for example
bis(2,3-epoxycyclopentyl)ether, 2,3-epoxy cyclopentyl glycidyl
ether, 1,2-bis(2,3-epoxycyclopentyloxy)ethane,
bis(4-hydroxycyclohexyl)methane diglycidyl ether and others. Any
type of photoinitiator that forms cations that initiate the
reactions of the epoxy and/or vinyl ether material(s) on exposure
to actinic radiation can be used. There are a large number of
suitable known cationic photoinitiators for epoxy and vinyl ether
resins. They include, for example, onium salts with anions of weak
nucleophilicity, halonium salts, iodosyl salts or sulfonium salts,
such as are disclosed in EP 153904 and WO 98/28663, sulfoxonium
salts, such as disclosed, for example, in EP 35969, EP 44274, EP
54509, and EP 164314, or diazonium salts, such as disclosed, for
example, in U.S. Pat. Nos. 3,708,296 and 5,002,856. Other cationic
photoinitiators are metallocene salts, such as disclosed, for
example, in EP 94914 and EP 94915. A survey of other current onium
salt initiators and/or metallocene salts can be found in "UV
Curing, Science and Technology" (Editor S. P. Pappas, Technology
Marketing Corp., 642 Westover Road, Stamford, Conn., U.S.A.) or
"Chemistry & Technology of UV & EB Formulation for
Coatings, Inks & Paints", Vol. 3 (edited by P. K. T. Oldring).
Specific examples of photo-cationic initiators include, for
example, mixed triarylsulfonium hexafluoroantimonate salts
(Cyracuree UVI-6974 and Cyracure.RTM. UVI-6990 photo-cationic
initiators, available from the Union Carbide Company),
diaryliodonium salts, such as the tetrafluoroborate,
hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate
salts, diphenyliodonium hexafluoroantimonate, triaryl sulfonium
salts, such as tetrafluoroborate, hexafluorophosphate,
hexafluoroarsenate and hexafluoroantimonate salts of
triphenylsulfonium, 4-tertiarybutyltriphenylsulfonium,
tris(4-methylphenyl)sulfonium, tris(4-methoxyphenyl)sulfonium, and
4-thiophenyltriphenylsulfonium, triphenylsulfonium
hexafluorophosphate and the like and mixtures thereof.
[0073] When the ink contains a component that cures upon
application of actinic radiation or UV light, the image-bearing
polymer sheet is irradiated with UV light or an electron beam to
cure the image on the polymeric sheet. The source of actinic
radiation may be selected from for example a low-pressure mercury
lamp, high-pressure mercury lamp, metal halide lamp, xenon lamp,
excimer laser, and dye laser for UV light, an electron beam
accelerator and the like. The dose is usually in the range of
50-3,000 mJ/cm.sup.2 for UV light and in the range of 0.2-1,000 mu
C/cm.sup.2 for electron beams.
[0074] Jet velocity, drop size and stability are greatly affected
by the surface tension and the viscosity of the ink. Inkjet inks
typically have a surface tension in the range of about 20 dyne/cm
to about 60 dyne/cm at 25.degree. C. Viscosity can be as high as 30
cP at 25.degree. C. The inks have physical properties compatible
with a wide range of ejecting conditions, i.e., driving frequency
of the piezo element, or ejection conditions for a thermal head,
for either a drop-on-demand device or a continuous device, and the
shape and size of the nozzle. It is preferable that the ink (as an
aqueous-based, non-aqueous-based or mixture of aqueous-based and
non-aqueous-based vehicles) has a sufficiently low viscosity such
that it can be jetted through the printing head of an ink jet
printer without the necessity of heating the print head. It is,
therefore, preferable for the ink viscosity to be below about 30
cP, as measured at 25.degree. C. More preferably, the ink viscosity
is below about 20 cP at 25.degree. C. For drop-on-demand ink jet
printers, it is preferable that the ink has a viscosity of above
about 1.5 cP at 25.degree. C. For drop-on-demand ink jet printers,
it is more preferable that the ink has a viscosity of above about
1.7 cP at 25.degree. C.
[0075] Any known ink jet printer process may be used to apply the
decoration to the polymer sheet. Specific examples of ink jet
printers include, for example, the HP Designjet inkjet printer, the
Purgatory inkjet printer, the Vutek UltraVu 3360 inkjet printer,
and the like. Printing heads useful for piezo electric processes
are available from, for example, Epson, Seiko-Epson, Spectra, XAAR
and XAAR-Hitachi. Printing heads useful for thermal ink jet
printing are available from, for example, Hewlett-Packard and
Canon. Printing heads suitable for continuous drop printing are
available, for example, from Iris and Video Jet.
[0076] Regardless of the process to apply the decoration on to the
polymeric sheet of the present invention, preferably the decoration
process is a rigid sheet process. An example of a rigid sheet
process includes a flatbed printing process equipped to handle
rigid sheet stock. Generally the stiff, high modulus physical
properties of the polymeric sheet of the present invention when
combined with the preferable sheet thickness does not allow the
storage of the sheet in roll form or of the take up of the
decorated sheet in roll form. This is in contradiction to the
teaching of the art for other decorated sheets. One significant
advantage of the sheet of the present invention is the avoidance of
the need for removable membranes or substrates or sacrificial webs
needed to mechanically stabilize the sheets of the art during the
printing operation to increase the sheets dimensional stability so
as to reduce or avoid color registration or misaligned color
placement issues. This provides a significant process
simplification. More preferably, the decoration is applied through
a rigid sheet digital printing process. Yet more preferably, the
decoration is applied through a rigid sheet ink jet printing
process.
[0077] As described above, the ink jet printing process allows for
the use of flat sheet stock which is not stored or fed from rolls
of sheet. The polymeric sheet of the present invention has a high
modulus and tends to be too stiff to be rolled. This is especially
true for polymeric sheet thicknesses of 30 mils (0.75 mm) or
greater of the present invention. As described above, the decorated
polymer sheet is preferably thick to provide the desirable
penetration strength of the high strength laminates produced from
therefrom through simplified and more efficient lamination
processes than found within the art. The enhanced penetration
strength is necessary within the present invention to satisfy many
of the current mandated requirements for hurricane and threat
resistance. Many enduses in the current environment require the
ethylene copolymer interlayer to be even thicker. Interlayers
thicker than 60 mils (1.50 mm), 90 mils (2.25 mm), and even thicker
than 120 mils (3.00 mm), are becoming commonplace within the
marketplace. It is further preferable that the decorated polymeric
sheet be thick to reduce the number of layers required within the
final laminate interlayer to provide the maximum lamination
efficiency. The greater thickness of the polymeric sheet further
allows for a simplification of the lamination process by
significantly reducing or eliminating the need for additional
interlayer sheets.
[0078] Ink jet printing processes which allows for the use of the
flat sheet stock of the present invention are known and are
generally flat bed ink jet printers. The manufacturers of flat bed
ink jet printers generally supply commercially available
modifications to allow for the printing of flat sheet stock, such
as the polymeric sheet of the present invention. Typically, the
printing process is of two general types. In one process, the flat
sheet stock is moved across the printhead(s) during the printing
process, generally through the use of rollers or through movement
of the entire flatbed that the sheet in immobilized in. In an
alternative process, the printhead(s) move across the sheet stock
immobilized in the flat bed. When UV-curable inksets are utilized,
the UV curing lamp is generally attached to the printhead(s).
[0079] Regardless of the process utilized to apply the image to the
polymer sheet, an adhesive or primer composition will preferably be
disposed on at least one surface, i.e. upper or lower surface, of
the sheet. At least a portion of the adhesive or primer composition
will contact at least a portion of the image. The adhesive layer is
preferably in the form of a coating, but it may also be a component
of the image-forming composition, for example a component of an
ink. When the adhesive/primer layer takes the form of an ink or
coating, the adhesive/primer coating is less than 1 mil thick.
Preferably, the adhesive/primer coating is less than 0.5 mil thick.
More preferably, the adhesive/primer coating is less than 0.1 mil
thick.
[0080] The adhesive or primer composition may comprise any adhesive
known in the art. The adhesive or primer composition enhances the
bond strength between the image disposed on the polymer sheet and
other materials, particularly to another layer in a laminate
structure. Mixtures of adhesives may also be utilized. Essentially
any adhesive or primer known will find utility within the present
invention.
[0081] Preferably, the adhesive composition is a silane which
incorporates an amine function. Specific examples of such materials
include, for example; gamma-aminopropyltriethoxysilane,
N-beta-(aminoethyl)-gamma-aminopropyl-trimethoxysilane, and the
like and mixtures thereof. Commercial examples of such materials
include, for example A-1100.RTM. silane (available from the
Silquest Company, and believed to be
gamma-aminopropyltrimethoxysilane) and Z6020.RTM. silane (available
from The Dow Chemical Company).
[0082] The adhesive composition may be applied to at least one
surface of polymer sheet through melt processes or through a
coating process, such as solution, emulsion, or dispersion coating.
Appropriate process parameters will be known to those of ordinary
skill in the art based on the type of adhesive composition used and
process selected for the application of the adhesive to the polymer
sheet surface. For example, when the ink does not comprise the
adhesive composition, the adhesive composition may be cast,
sprayed, air knifed, brushed, rolled, poured, printed or the like
onto the polymer sheet surface after application of the image to
the polymer sheet. Generally the adhesive composition will be
diluted with a liquid prior to application and applied as a liquid
medium to provide uniform coverage over the surface of the polymer
sheet. The liquid may comprise one or more components and function
as a solvent for the adhesive composition to form a solution or may
function as a non-solvent for the adhesive composition to form a
dispersion or emulsion. Usable liquids which may serve as solvents
or non-solvents include those described above for the ink
compositions.
[0083] The second layer of the laminates of the present invention
comprises a film. The films can be composed of any polymer known
that can be used in a laminate of the present invention without
detriment to the intended use. The polymers may be thermoplastic
resins or elastomers, and include polymeric materials found in
nature. This should not be considered limiting. Essentially any
polymer may find utility as the film resin of the present
invention.
[0084] Preferably, the polymeric film is transparent. More
preferable polymeric film materials include, without limitation,
poly(ethylene terephthalate), polycarbonate, polypropylene,
polyethylene, polypropylene, cyclic polyolefins, norbornene
polymers, polystyrene, syndiotacetic polystyrene, styrene-acrylate
copolymers, acrylonitrile-styrene copolymers, poly(ethylene
naphthalate), polyethersulfone, polysulfone, nylons,
poly(urethanes), acrylics, cellulose acetates, cellulose
triacetates, cellophane, vinyl chloride polymers, polyvinyl
fluoride, polyvinylidene fluoride and the like. Still more
preferably, the polymeric film is biaxially oriented poly(ethylene
terephthalate) film.
[0085] Preferably, one or both surfaces of the polymeric film may
be treated to enhance the adhesion to the polymeric sheet. This
treatment may take any form known within the art, including
adhesives, primers, such as silanes, flame treatments, such as
disclosed within U.S. Pat. No. 2,632,921, U.S. Pat. No. 2,648,097,
U.S. Pat. No. 2,683,894, and U.S. Pat. No. 2,704,382, plasma
treatments, such as disclosed within U.S. Pat. No. 4,732,814,
electron beam treatments, oxidation treatments, corona discharge
treatments, chemical treatments, chromic acid treatments, hot air
treatments, ozone treatments, ultraviolet light treatments, sand
blast treatments, solvent treatments, and the like and combinations
thereof. For example, a thin layer of carbon may be deposited on
one or both surfaces of the polymeric film through vacuum
sputtering as disclosed in U.S. Pat. No. 4,865,711. For example,
U.S. Pat. No. 5,415,942 discloses a hydroxy-acrylic hydrosol primer
coating that may serve as an adhesion-promoting primer for
poly(ethylene terephthalate) films.
[0086] Preferably, the polymeric film of the present invention
includes a primer coating on one or both surfaces, more preferably
both surfaces, comprising a coating of a polyallylamine-based
primer. The polyallylamine-based primer and its application to a
poly(ethylene terephthalate) polymeric film are disclosed within
U.S. Pat. No. 5,411,845, U.S. Pat. No. 5,770,312, U.S. Pat. No.
5,690,994, and U.S. Pat. No. 5,698,329. Generally, the
poly(ethylene terephthalate) film is extruded and cast as a film by
conventional methods, as described above, and the polyallylamine
coating is applied to the poly(ethylene terephthalate) film either
before stretching or between the machine direction stretching and
transverse direction stretching operations, and/or after the two
stretching operations and heat setting in the stenter oven. It is
preferable that the coating be applied before the transverse
stretching operation so that the coated poly(ethylene
terephthalate) web is heated under restraint to a temperature of
about 220.degree. C. in the stenter oven in order to cure the
polyallylamine to the poly(ethylene terephthalate) surface(s). In
addition to this cured coating, an additional polyallylamine
coating can be applied on it after the stretching and stenter oven
heat setting in order to obtain a thicker overall coating.
[0087] The thickness of the polymeric film is not critical and may
be varied depending on the particular application. Generally, the
thickness of the polymeric film will range from about 0.1 mils
(0.003 mm), to about 10 mils (0.26 mm). For automobile windshields,
the polymeric film thickness may be preferably within the range of
about 1 mil (0.025 mm), to about 4 mils (0.1 mm).
[0088] The polymeric film is preferably sufficiently
stress-relieved and shrink-stable under the coating and lamination
processes. Preferably, the polymeric film is heat stabilized to
provide low shrinkage characteristics when subjected to elevated
temperatures (i.e. less than 2 percent shrinkage in both directions
after 30 minutes at 150 C), such are seen through the lamination
processes described below.
[0089] Preferably, the second layer of the laminates of the present
invention comprises a solar control film. As used herein the term
"solar control film" means a film which can reflect or absorb
infrared light. The solar control film that forms the second layer
of the laminate of the invention may reflect infrared light or
absorb infrared light. In certain instances the film may both
reflect and absorb infrared light due to the particular additives
present in the film or coatings applied to the film.
[0090] The major component of the solar control films is at least
one polymeric material. The polymers may be thermoplastic resins or
elastomers, and may include polymeric materials found in nature, as
are described above for the films.
[0091] One useful class of solar control films is characterized by
the presence of indium tin oxide as a component of the film or as a
coating on the film surface. Polymeric films coated with indium tin
oxide nanoparticles incorporated within a matrix material are
commercially available. For example, the Tomoegawa Paper Company,
Ltd., of Tokyo, Japan, offers a line of solar control films within
their Soft Look.RTM. film product offering. The Soft Look.RTM.
solar control films incorporate indium tin oxide nanoparticles
dispersed within a matrix material and solution coated on biaxially
stretched poly(ethylene terephthalate) film. The Soft Look.RTM.
solar control films also incorporate a UV shielding hard coat layer
in contact with the indium tin oxide infrared shielding layer and
may further incorporate adhesive layers as the outer layers of the
films. Typical examples of such films are characterized by having a
visible radiation transmittance of 85.80 percent, sunlight
radiation transmittance of 68.5 percent, a sunlight reflectance of
7.9 percent, and a screening factor of 0.86. Soft Look.RTM. solar
control films are also typically hardcoated to improve the abrasion
resistance. Specific grades of Soft Look.RTM. solar control films
include Soft Look.RTM. UV/IR 25 solar control film and Soft
Look.RTM. UV/IR 50 solar control film.
[0092] Another useful class of solar control films suitable for use
as the second layer of the laminates of the invention includes
polymeric films having antimony tin oxide as a component of the
film or present in a coating on the film surface. Polymeric films
coated with antimony tin oxide nanoparticles incorporated within a
matrix material known as RAYBARRIER.RTM. films are commercially
available from the Sumitomo Osaka Cement Company. RAYBARRIER.RTM.
solar control films incorporate antimony tin oxide nanoparticles
with a nominal particle size of about 10 nm dispersed within a
matrix material and coated on biaxially stretched poly(ethylene
terephthalate) film. Typical optical properties of these control
films include a visible radiation transmittance of 78.9 percent,
sunlight radiation transmittance of 66.0 percent, a sunlight
reflectance of 8.4 percent, a UV transmittance of 0.4 percent, and
a screening factor of 0.8. The RAYBARRIER.RTM. solar control films
are also typically hardcoated to improve the abrasion resistance
with typical values of a delta H (defined as the haze difference of
before and after the Taber abrasion test) of 4.9 percent within a
Taber abrasion test (abrasion wheel: CS-10F, Load: 1000 grams and
abrasion cycle: 100 cycles). Specific grades of RAYBARRIER.RTM.
solar control films include RAYBARRIER.RTM. TFK-2583 solar control
film with a visible radiation transmittance of 81.6 percent, a
sunlight radiation transmittance of 66.8 percent and a haze value
of 1.1 percent, RAYBARRIER.RTM. TFM-5065 solar control film with a
visible radiation transmittance of 67.1 percent, a sunlight
radiation transmittance of 47.5 percent and a haze value of 0.4
percent, RAYBARRIER.RTM. SFJ-5030 solar control film with a visible
radiation transmittance of 29.2 percent, a sunlight radiation
transmittance of 43.0 percent and a haze value of 1.0 percent,
RAYBARRIER.RTM. SFI-5010 solar control film with a visible
radiation transmittance of 12.0 percent, a sunlight radiation
transmittance of 26.3 percent and a haze value of 0.8 percent,
RAYBARRIER.RTM. SFH-5040 solar control film with a visible
radiation transmittance of 41.5 percent, a sunlight radiation
transmittance of 41.9 percent and a haze value of 0.7 percent and
RAYBARRIER.RTM. SFG-5015 solar control film with a visible
radiation transmittance of 14.8 percent, a sunlight radiation
transmittance of 20.9 percent and a haze value of 0 percent.
[0093] Another suitable class of solar control films that may be
used as the second layer of the laminate of the invention includes
polymeric films which incorporate lanthanum hexaboride
nanoparticles as a component or a coating. Commercially available
examples are available from the Sumitomo Metal Mining Company of
Tokyo, Japan. One type incorporates lanthanum hexaboride
nanoparticles.
[0094] The solar control films may further incorporate other
absorptive materials, such as, for example, organic infrared
absorbents, for example, polymethine dyes, amminium dyes, imminium
dyes, dithiolene-type dyes and phthalocyanine-type dyes and
pigments. Combinations of such additives are also useful as
components of the solar control film.
[0095] Although the solar control film that forms the second layer
of the laminate may reflect infrared light or absorb infrared
light, preferably the solar control film reflects infrared light.
Reflective films are metallized polymeric films and include any
film with an infrared energy reflective layer. Thus, the second
layer may be a simple semi-transparent metal layer or it may
comprise a series of metal/dielectric layers. Such stacks are
commonly referred to as interference filters of the Fabry-Perot
type. Each layer may be angstrom-thick or thicker. The thickness of
the various layers in the filter is controlled to achieve an
optimum balance between the desired infrared reflectance while
maintaining visible light transmittance. The metal layers are
separated by (i.e. sandwiched between) one or more dielectric
layers. Reflection of visible light from the metal layers
interferes destructively, thereby enhancing visible light
transmission. Suitable metals for the metal layers include, for
example, silver, palladium, aluminum, chromium, nickel, copper,
gold, zinc, tin, brass, stainless steel, titanium nitride and
alloys or claddings thereof. For optical purposes, silver and
silver-gold alloys are preferred. Metal layer thickness are
generally in the range of from about 60 to about 200 .ANG.,
preferably within the range from about 80 to about 140 .ANG.. In
general, the dielectric material should be chosen with a refractive
index greater than that of the laminate layer it contacts. In
general, a higher refractive index of the dielectric layers is
desirable. Preferably, the dielectric material will have a
refractive index of greater than about 1.8. More preferably, the
dielectric material will have a refractive index of greater than
about 2.0. The dielectric layer material should be transparent over
the visible range and at least one dielectric layer must exist
between a pair of metal layers. Suitable dielectric materials for
the dielectric layers include, for example; zirconium oxide,
tantalum oxide, tungsten oxide, indium oxide, tin oxide, indium tin
oxide, aluminum oxide, zinc sulfide, zinc oxide, magnesium
fluoride, niobium oxide, silicon nitride, and titanium oxide.
Preferable dielectric materials include tungsten oxide, indium
oxide, tin oxide, and indium tin oxide. Generally, the layers are
formed through vacuum deposition processes, such as vacuum
evaporation processes or sputtering deposition processes. Examples
of such processes include resistance heated, laser heated or
electron-beam vaporization evaporation processes and DC or RF
sputtering processes (diode and magnetron) under normal and
reactive conditions. Preferably, the reflective layer is made up of
one or more semi-transparent metal layers bounded on each side by
transparent dielectric layers. One form known as an interference
filter comprises at least one layer of reflective metal sandwiched
between reflection-suppressing or anti-reflective dielectric
layers. These layers are usually arranged in sequence as stacks
carried by an appropriate transparent planar substrate such as a
biaxially oriented polyethylene terephthalate film. These layers
can be adjusted to reflect particular wave lengths of energy, in
particular heat and other infrared wavelengths, as disclosed in
U.S. Pat. Nos. 4,799,745 and 4,973,511. Varying the thickness and
composition of a dielectric layer spaced between two reflecting
metal layers will vary the optical transmittance/reflection
properties considerably. More specifically, varying the thickness
of the spacing dielectric layer varies the wave length associated
with the reflection suppression (or transmission enhancement)
band.
[0096] In addition to the choice of metal, thickness also
determines reflectivity. Generally, the thinner the layer, the less
is its reflectivity. Generally, the thickness of the spacing
dielectric layer(s) is between about 200 to about 1200 .ANG.,
preferably between about 450 to about 1000 .ANG., to obtain the
desired optical properties. The preferred dielectric stack for
automotive uses contains at least two near infrared reflecting
metal layers. In the operative position such stacks transmit at
least 70 percent visible light of normal incidence measured as
specified in ANSI Z26.1. Architectural applications may utilize
dielectric stacks with lower levels of visible light transmittance.
Preferably, visible light reflectance from the surface of the stack
is less than about 8 percent. Exterior dielectric layers in contact
with the metal layer surfaces opposite to the metal surfaces
contacting spacing dielectric layers further enhances
anti-reflection performance. The thickness of such exterior or
outside dielectric layers is generally about 20 to about 600 .ANG.,
preferably about 50 to about 500 .ANG..
[0097] Metal dielectric constructs are manufactured commercially,
for example by Southwall Technologies, Inc. Constructs are
available as laminated and non-laminated structures with silver and
silver/gold as the metal and indium oxide and indium tin oxide as
the dielectric. Specific examples include XIR.RTM. 70, which has a
70 percent visible light transmittance, a 9 percent visible light
reflectance (exterior), a 46 percent total solar transmittance, a
22 percent solar reflectance (exterior), a relative heat gain of
117 and greater than 99 percent ultraviolet blockage and XIR.RTM.
75, which has a 75 percent visible light transmittance, a 11
percent visible light reflectance (exterior), a 52 percent total
solar transmittance, a 23 percent solar reflectance (exterior), a
relative heat gain of 135 and greater than 99 percent ultraviolet
blockage when placed in a 2.1 mm clear glass/XIR.RTM.
film/polyvinyl butyral interlayer/2.1 mm clear glass
construction.
[0098] Preferably, one or both surfaces of the solar control film
may be treated to enhance the adhesion to a coating or to the
image-bearing polymer sheet of the invention or both, as described
above for the polymeric films.
[0099] The thickness of the solar control film that forms the
second layer of the laminate of the invention is not critical and
may be varied depending on the particular application. The
thickness of the film will generally range from about 0.1 mils
(0.003 mm), to about 10 mils (0.26 mm). In embodiments useful for
automobile windshields, the solar control film thickness is
preferably within the range of about 1 mil (0.025 mm) to about 4
mils (0.1 mm).
[0100] The solar control film is preferably sufficiently
stress-relieved and shrink-stable under the coating and lamination
process conditions. Preferably, the polymeric film is heat
stabilized to provide low shrinkage characteristics when subjected
to elevated temperatures (i.e. less than 2 percent shrinkage in
both directions after 30 minutes at 150.degree. C.).
[0101] The laminates of the present invention may optionally
include additional layers, such as other polymeric sheets, other
uncoated polymeric films, such as biaxially oriented polyethylene
terephthalate film, and other coated polymeric films. Examples of
other polymeric sheets would include those produced from materials
with a modulus of 20,000 psi (138 MPa) or less as measured by ASTM
Method D-638-03 or greater than 20,000 psi. The polymeric film and
sheets of the additional layer or layers may provide additional
attributes, such as acoustical barriers. Polymeric films and sheets
which provide acoustical dampening include, for example, ethylene
vinyl acetate copolymers, ethylene methyl acrylate copolymers,
plasticized polyvinyl chloride resins, metallocene-catalyzed
polyethylene compositions, polyurethanes, polyvinyl butyral
compositions, highly plasticized polyvinyl butyral compositions,
silicone/acrylate ("ISD") resins, and the like. Such "acoustic
barrier" resins are disclosed in U.S. Pat. Nos. 5,368,917;
5,624,763; 5,773,102; and 6,432,522. Preferably, the polymeric film
or sheet of the additional layer or layers is formed of a polymer
selected from the group consisting of polycarbonate, polyurethane,
acrylic sheets, polymethylmethacrylate, polyvinyl chloride,
polyester, poly(ethylene-co-(meth)acrylic acid) ionomers and
biaxially oriented poly(ethylene terephthalate). Adhesives or
primers may be applied to the additional film layers, especially to
provide adequate adhesion between the additional polymeric layer
film layer or layers and the image-bearing polymer sheet layer
and/or solar control film layers of the laminates of the present
invention.
[0102] Preferred embodiments include laminate constructions which
incorporate at least one image-bearing polymer sheet layer (i.e. a
polymer sheet having an image disposed thereon) of the invention
and at least one film or solar control film layer; laminates which
incorporate at least one image-bearing polymer sheet layer of the
invention and at least two film layers; laminates which incorporate
at least one image-bearing polymer sheet layer of the invention, at
least one other sheet layer and at least one film or solar control
film layer; laminates which incorporate at least one rigid sheet
layer, at least one image-bearing polymer sheet layer of the
invention and at least one film or solar control film layer;
laminates which incorporate at least one rigid sheet layer, at
least one image-bearing polymer sheet layer of the invention, at
least one other sheet layer and at least one film or solar control
film layer; laminates which incorporate at least two rigid sheet
layers and at least one image-bearing polymer sheet layer of the
invention and at least one film or solar control film layer;
laminates which incorporate at least two rigid sheet layers, at
least one image-bearing polymer sheet layer of the invention and at
least one other sheet layer and at least one film or solar control
film layer; and laminates which incorporate at least two rigid
sheet layers, at least one image-bearing sheet layer of the
invention, at least one other sheet layer and at least one film or
solar control film layer.
[0103] The rigid sheet layers may be glass or rigid transparent
plastic sheets, such as, for example, polycarbonate, acrylics,
polyacrylate, cyclic polyolefins, such as ethylene norbornene
polymers, metallocene-catalyzed polystyrene and the like. Blends of
such materials may also form the rigid sheet. Metal or ceramic
plates may be substituted for the rigid polymeric sheet or glass if
clarity is not required for the laminate. The term "glass" as used
herein includes not only window glass, plate glass, silicate glass,
sheet glass and float glass, but also includes colored glass,
specialty glass which includes ingredients to control, for example,
solar heating, coated glass with, for example, sputtered metals,
such as silver or indium tin oxide, for solar control purposes,
E-glass, Toroglass, Solex.RTM. glass and the like. Such specialty
glasses are disclosed in U.S. Pat. Nos. 4,615,989; 5,173,212;
5,264,286; 6,150,028; 6,340,646; 6,461,736; and 6,468,934. The type
of glass to be selected for a particular laminate depends on the
intended use. Within any of the above embodiments, the rigid sheets
may be substituted independently for any other type of rigid
sheet.
[0104] The laminate layers (also known as plies) may be combined
during extrusion or finishing processes resulting in production of
laminates with improved physical characteristics. Five or more
separate layers are not uncommon. Adhesive or tie layers are often
present in such laminates.
[0105] The processes which may be used to produce the laminates of
the present invention are numerous and various. In the simplest
process, the decorated polymer sheet of the invention is contacted
with a second film or solar control film, for example by laying the
second film atop the surface of the polymer sheet of the invention
upon which the image is disposed.
[0106] Typically, pressure will be applied during formation of the
laminate. One process useful to produce a laminate comprising the
image-bearing polymeric sheet of the invention laminated to a
polymeric film (coated or uncoated) comprises steps of lightly
bonding the sheet to the film through a nip roll bonding process.
In such a process, polymeric film is supplied from a roll and first
passes over a tension roll. The film may be subjected to moderate
heating by passing through a heating zone, such as an oven. The
image-bearing polymeric sheet may also be supplied from a roll or
as flat sheet stock and will typically first pass over a tension
roll. The image-bearing polymeric sheet may be subjected to
moderate heating by passing through a heating zone, such as an
oven. Heating the film and sheet to a temperature sufficient to
promote temporary fusion bonding, i.e. to cause the surfaces of the
image-bearing polymeric sheet to become tacky, is useful. Suitable
temperatures for the image-bearing polymeric sheets of the
invention will be within the range of about 50.degree. C. to about
120.degree. C., with the preferred surface temperatures reaching
about 65.degree. C. The film is fed along with the image-bearing
polymeric sheet through nip rolls where the two layers are merged
together under moderate pressure to form a weakly bonded laminate.
If desired, the nip rolls may be heated to promote the bonding
process. The bonding pressure exerted by the nip rolls may vary
with the film materials, the image-bearing polymeric sheet
materials, and the temperatures employed. Generally the bonding
pressure will be within the range of about 10 psi (0.7 kg/sq cm) to
about 75 psi (5.3 kg/sq cm) and is preferably within the range of
about 25 psi (1.8 kg/sq cm) to about 30 psi (2.1 kg/sq cm). The
tension of the image-bearing polymeric sheet/film laminate is
controlled by passage over an idler roll. Typical line speeds
through the roll assembly are within the range of about 5 feet (1.5
m) to about 30 feet (9.2 m) per minute. Proper control of the speed
and the tension tends to minimize wrinkling of the film. After
bonding, the laminate is passed over a series of cooling rolls
which ensure that the laminate taken up on a roll is not tacky.
Tension within the system may be further maintained through the use
of idler rolls. Laminates made according to this process will have
sufficient strength to allow handling by laminators who may produce
further laminates, such as glass laminates, which encapsulate this
two-layer laminate. This process may be modified to produce a wide
variety of laminate types. For example, the film may be
encapsulated between the image-bearing polymeric sheet of the
invention and another polymeric sheet by the addition of another
polymeric sheet to the above process; the image-bearing polymeric
sheet may be encapsulated between two polymeric films by the
addition of a second film; the image-bearing polymeric sheet may be
encapsulated between a polymeric film and another polymeric sheet
through the addition of another polymeric sheet; and so forth.
Adhesives and primers may be used to enhance the bond strength
between the laminate layers, if desired.
[0107] If an adhesive layer is present, it is preferably in the
form of a coating. The adhesive may be any adhesive or primer known
in the art, as described above. The adhesives and primers may be
used, for example, to enhance the bond strength between the
decorated surface of the image-bearing polymer sheet layer and the
other laminate layers.
[0108] The laminates of the present invention may also be produced
through autoclave processes. In a typical autoclave process, a
glass sheet, a laminate of the invention composed of a decorated
polyvinyl butyral sheet (i.e. having an image disposed on a
surface), a metallized film, a second polyvinyl butyral sheet and a
second glass sheet are laminated together under heat and pressure
and a vacuum (for example, in the range of about 27-28 inches
(689-711 mm) Hg), to remove air. Preferably, the glass sheets have
been washed and dried. A typical glass type is 90 mil thick
annealed flat glass. In a typical procedure, the laminate of the
present invention is positioned between two glass plates to form a
glass/interlayer/glass assembly, placing the assembly into a bag
capable of sustaining a vacuum ("a vacuum bag"), the air is drawn
out of the bag using a vacuum line, the bag is sealed while
maintaining the vacuum and the sealed bag is placed in an autoclave
at a temperature of about 130.degree. C. to about 180.degree. C.,
at a pressure of about 200 psi (15 bars), for from about 10 to
about 50 minutes. Preferably the bag is autoclaved at a temperature
of from about 120.degree. C. to about 160.degree. C. for 20 minutes
to about 45 minutes. More preferably, the bag is autoclaved at a
temperature of from about 135.degree. C. to about 160.degree. C.
for 20 minutes to about 40 minutes. Most preferably, the bag is
autoclaved at a temperature of from about 145.degree. C. to about
155.degree. C. for 25 minutes to about 35 minutes. A vacuum ring
may be substituted for the vacuum bag. One type of vacuum bag is
disclosed in U.S. Pat. No. 3,311,517. Alternatively, other
autoclave processes may be used to produce the laminates of the
present invention. Any air trapped within the
glass/interlayer/glass assembly may be removed through a nip roll
process. For example, the glass/interlayer/glass assembly may be
heated in an oven at between about 80.degree. C. and about
120.degree. C., preferably between about 90.degree. C. and about
100.degree. C., for about 30 minutes. Thereafter, the heated
glass/interlayer/glass assembly is passed through a set of nip
rolls so that air in the void spaces between the glass and the
polymer may be squeezed out, and the edge of the assembly sealed.
This type of assembly is commonly referred to in the art as a
pre-press. The pre-press may then be placed in an air autoclave
where the temperature is raised to between about 120.degree. C. and
about 160.degree. C., preferably between about 135.degree. C. and
about 160.degree. C., and pressure to between about 100 psig to
about 300 psig, preferably about 200 psig (14.3 bar). These
conditions are maintained for about 15 minutes to about 1 hour,
preferably about 20 minutes to about 50 minutes, after which the
air is cooled and no further air is added to the autoclave. After
about 20 minutes of cooling, venting occurs and the laminates are
removed from the autoclave.
[0109] The laminates of the present invention may also be produced
through non-autoclave processes. Such non-autoclave processes are
disclosed, for example, in U.S. Pat. Nos. 3,234,062; 3,852,136;
4,341,576; 4,385,951; 4,398,979; 5,536,347; 5,853,516; 6,342,116;
5,415,909; U.S. Published Patent Application 2004/0182493, European
Patent 1 235 683 B1, PCT Publication WO 91/01880 and PCT
Publication WO 03/057478 A1. Generally, non-autoclave processes
include heating the pre-press assembly and the application of
vacuum, pressure or both. For example, the pre-press may be
successively passed through heating ovens and nip rolls.
[0110] As one skilled in the art will appreciate, the above
processes may be easily modified to make a wide variety of
laminates. For example, laminates which incorporate at least one
rigid sheet layer, at least one decorated sheet layer (i.e. a
polymeric sheet layer on which an image is disposed, also referred
to herein as an image-bearing polymer sheet) and at least one film
or solar control film layer; laminates which incorporate at least
one rigid sheet layer, at least one decorated sheet layer, at least
one other sheet layer and at least one film or solar control film
layer; laminates which incorporate at least two rigid sheet layers
and at least one decorated sheet layer and at least one film or
solar control film; laminates which incorporate at least two rigid
sheet layers, at least one decorated sheet layer and at least one
other sheet layer and at least one film or solar control film;
laminates which incorporate at least two rigid sheet layers, at
least one decorated sheet layer, at least one other sheet layer and
at least one film or solar control film layer; and the like may be
produced. The rigid sheets may be substituted independently for any
other type of rigid sheet. These embodiments may be produced
according to any of the non-autoclave processes described
herein.
[0111] The decorated polymer sheets and laminates of the present
invention are useful in glazing applications such as: architectural
glass; signage; privacy glass; decorative glass walls; decorative
glass dividers; windows in buildings; windshields and sidelites in
automobiles, planes, trains and the like; structural support units
such as stairs, floors, walls, partitions; other architectural
units such as ceilings. Laminates of the present invention are
particularly useful in applications where high strength and high
penetration resistant safety glass is desirable or required. One of
ordinary skill in the art of glazing manufacture, or glass
lamination for safety glass applications would know and appreciate
the various uses and applications of the resins and laminates
described herein.
[0112] The following examples are presented for illustrative
purposes only, and are not intended to limit the scope of the
invention in any manner.
EXAMPLE 1
[0113] An ink set is prepared that consists of the ink formulations
shown in Table I where percentages are based on the total weight of
the ink formulation. The pigment dispersion compositions and
preparations are as disclosed in the Examples of U.S. Published
Patent Application 2004/0187732. TABLE-US-00001 TABLE I Magenta
36.08 wt. % of a magenta pigment dispersion (7 wt. % pigment) 38.35
wt. % Dowanol .RTM. DPMA.sup.1 25.57 wt. % Dowanol .RTM. DPnP.sup.1
Yellow 35.23 wt. % of a yellow pigment dispersion (7 wt. % pigment)
38.86 wt. % Dowanol .RTM. DPMA.sup.1 25.91 wt. % Dowanol .RTM.
DPnP.sup.1 Cyan 28.35 wt. % of a cyan pigment dispersion (5.5 wt. %
pigment) 42.99 wt. % Dowanol .RTM. DPMA.sup.1 28.66 wt. % Dowanol
.RTM. DPM.sup.1 Black 27.43 weight percent of a black pigment
dispersion (7 weight percent pigment) 43.54 weight percent Dowanol
.RTM. DPMA.sup.1 29.03 weight percent Dowanol .RTM. DPM.sup.1
.sup.1Available from The Dow Chemical Company
[0114] Using the above mentioned ink set, a 30 mil thick (0.75 mm)
SentryGlas.RTM. Plus sheet (a product of the DuPont Company) is ink
jet printed with a decoration with a NUR Tempo.RTM. Modular Flatbed
Inkjet Presses equipped to handle rigid sheet stock manufactured by
NUR Microprinters of Monnachie, N.J., to provide a ink coverage of
25 percent.
[0115] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, a surface flame-treated, biaxially
oriented poly(ethylene terephthalate) (PET) film, a SentryGlas.RTM.
Plus sheet (a product of the DuPont Company), and a glass layer are
produced in the following manner. The decorated sheets from above
(12 inches by 12 inches (305 mm.times.305 mm)), the surface
flame-treated, biaxially oriented PET film (12 inches by 12 inches
(305 mm.times.305 mm) by 4 mils (0.10 mm) thick), and the
SentryGlas.RTM. Plus sheets (12 inches by 12 inches (305
mm.times.305 mm) by 30 mils (0.75 mm) thick), are conditioned at 23
percent relative humidity (RH), at a temperature of 72 degrees F.
overnight. The samples are laid up with a clear annealed float
glass plate layer (12 inches by 12 inches (305 mm.times.305 mm) by
2.5 mm thick), a decorated sheet layer from above, a surface
flame-treated PET film layer, a SentryGlas.RTM. Plus sheet layer
and a clear annealed float glass plate layer (12 inches by 12
inches (305 mm.times.305 mm) by 2.5 mm thick). The
glass/interlayer/glass assembly is then placed into a vacuum bag
and heated to 90-100 C for 30 minutes to remove any air contained
between the glass/interlayer/glass assembly. The
glass/interlayer/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/glass
laminate is removed from the autoclave.
EXAMPLE 2
[0116] A 60 mil thick (1.50 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 4-color CMYK UV-curable
inkset available from NUR Microprinters to provide a ink coverage
of 50 percent.
[0117] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, and a surface flame-treated, biaxially
oriented poly(ethylene terephthalate) (PET) film are produced in
the following manner. The decorated sheets from above (12 inches by
12 inches (305 mm.times.305 mm)), and the surface flame-treated,
biaxially oriented PET film (12 inches by 12 inches (305
mm.times.305 mm) by 4 mils (0.10 mm) thick), are conditioned at 23
percent relative humidity (RH), at a temperature of 72 degrees F.
overnight. The samples are laid up with a clear annealed float
glass plate layer (12 inches by 12 inches (305 mm.times.305 mm) by
2.5 mm thick), a decorated sheet layer from above, a surface
flame-treated PET film layer, a thin Teflon.RTM. film layer (12
inches by 12 inches (305 mm.times.305 mm)), and an annealed float
glass layer (12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm
thick). The glass/interlayer/PET film/Teflon.RTM. film/glass
assembly is then placed into a vacuum bag and heated to 90-100 C
for 30 minutes to remove any air contained between the
glass/interlayer/PET film/Teflon.RTM. film/glass assembly. The
glass/interlayer/PET film/Teflon.RTM. film/glass pre-press assembly
is then subjected to autoclaving at 135 C for 30 minutes in an air
autoclave to a pressure of 200 psig (14.3 bar), as described above.
The air is then cooled while no more air is added to the autoclave.
After 20 minutes of cooling when the air temperature is less than
about 50 C, the excess pressure is vented, and the
glass/interlayer/PET film/Teflon.RTM. film/glass laminate is
removed from the autoclave. Removal of the glass cover sheet and
the thin Teflon.RTM. film provides the glass/decorated
sheet/polyester film laminate of the present invention.
EXAMPLE 3
[0118] A 90 mil thick (2.25 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 4-color CMYK UV-curable
inkset and a UV-curable white ink available from NUR Microprinters
to provide a ink coverage of 100 percent.
[0119] A solution of A-1100 silane (0.025 weight percent based on
the total weight of the solution, a product of the Silquest
Company, believed to be gamma-aminopropyltrimethoxysilane),
isopropanol (66.65 weight percent based on the total weight of the
solution), and water (33.32 weight percent based on the total
weight of the solution), is prepared and allowed to sit for at
least one hour prior to use. A 12-inch by 12-inch piece of the
decorated SentryGlas.RTM. Plus sheet from above is dipped into the
silane solution (residence time of about 1 minute), removed and
allowed to drain and dry under ambient conditions.
[0120] Glass laminates composed of a glass layer, the silane primed
decorated sheet interlayer from above, a poly(allyl amine) primed,
biaxially oriented poly(ethylene terephthalate) (PET) film, a
SentryGlas.RTM. Plus sheet (a product of the DuPont Company), and a
glass layer are produced in the following manner. The silane primed
decorated sheets from above (12 inches by 12 inches (305
mm.times.305 mm)), the poly(allyl amine) primed, biaxially oriented
PET film (12 inches by 12 inches (305 mm.times.305 mm) by 4 mils
(0.10 mm) thick), and the SentryGlas.RTM. sheets (12 inches by 12
inches (305 mm.times.305 mm) by 60 mils (1.50 mm) thick), are
conditioned at 23 percent relative humidity (RH), at a temperature
of 72 degrees F. overnight. The samples are laid up with a clear
annealed float glass plate layer (12 inches by 12 inches (305
mm.times.305 mm) by 2.5 mm thick), a silane primed decorated sheet
layer from above, a poly(allyl amine) primed PET film layer, a
SentryGlas.RTM. Plus sheet layer and a clear annealed float glass
plate layer (12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm
thick). The glass/interlayer/glass assembly is then placed into a
vacuum bag and heated to 90-100 C for 30 minutes to remove any air
contained between the glass/interlayer/glass assembly. The
glass/interlayer/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/glass
laminate is removed from the autoclave.
EXAMPLE 4
[0121] A 120 mil thick (3.00 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 6-color CMYK+IcIm UV-curable
inkset and a UV-curable white ink available from NUR Microprinters
to provide a ink coverage of 200 percent.
[0122] A solution of A-1100 silane (0.10 weight percent based on
the total weight of the solution, a product of the Silquest
Company, believed to be gamma-aminopropyltrimethoxysilane), acetic
acid (0.01 weight percent based on the total weight of the
solution), isopropanol (66.59 weight percent based on the total
weight of the solution), and water (33.30 weight percent based on
the total weight of the solution), is prepared. A 12-inch by
12-inch piece of the decorated SentryGlas.RTM. Plus sheet from
above is dipped into the silane solution (residence time of about 1
minute), removed and allowed to drain and dry under ambient
conditions.
[0123] Glass laminates composed of a glass layer, the silane primed
decorated sheet interlayer from above, and a XIR.RTM.-70 HP Auto
film (a product of the Southwall Company), are produced in the
following manner. The silane primed decorated sheets from above (12
inches by 12 inches (305 mm.times.305 mm)), and the XIR.RTM.-70 HP
Auto films (12 inches by 12 inches (305 mm.times.305 mm), by 2 mils
(0.05 mm) thick), are conditioned at 23 percent relative humidity
(RH), at a temperature of 72 degrees F. overnight. The samples are
laid up with a clear annealed float glass plate layer (12 inches by
12 inches (305 mm.times.305 mm) by 2.5 mm thick), a silane primed
decorated sheet layer from above, a XIR.RTM.-70 HP Auto film layer
(with the metallized surface of the XIR.RTM.-70 HP Auto film in
contact with the decorated sheet layer), a thin Teflon.RTM. film
layer (12 inches by 12 inches (305 mm.times.305 mm)), and an
annealed float glass layer (12 inches by 12 inches (305
mm.times.305 mm) by 2.5 mm thick). The glass/interlayer/XIR.RTM.-70
HP Auto film/Teflon.RTM. film/glass assembly is then placed into a
vacuum bag and heated to 90-100 C for 30 minutes to remove any air
contained between the glass/interlayer/XIR.RTM.-70 HP Auto
film/Teflon.RTM. film/glass assembly. The
glass/interlayer/XIR.RTM.-70 HP Auto film/Teflon.RTM. film/glass
pre-press assembly is then subjected to autoclaving at 135 C for 30
minutes in an air autoclave to a pressure of 200 psig (14.3 bar),
as described above. The air is then cooled while no more air is
added to the autoclave. After 20 minutes of cooling when the air
temperature is less than about 50 C, the excess pressure is vented,
and the glass/interlayer/XIR.RTM.-70 HP Auto film/Teflon.RTM.
film/glass laminate is removed from the autoclave. Removal of the
glass cover sheet and the thin Teflon.RTM. film provides the
glass/decorated sheet/XIR.RTM.-70 HP Auto film laminate of the
present invention.
EXAMPLE 5
[0124] A 30 mil thick (0.75 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 8-color CMYK+IcImIyIk
UV-curable inkset available from NUR Microprinters to provide a ink
coverage of 400 percent.
[0125] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, a XIR.RTM.-75 Auto Blue V-1 film (a
product of the Southwall Company), a SentryGlas.RTM. Plus sheet (a
product of the DuPont Company), and a glass layer are produced in
the following manner. The decorated sheets from above (12 inches by
12 inches (305 mm.times.305 mm)), the XIR.RTM.-75 Auto Blue V-1
films (12 inches by 12 inches (305 mm.times.305 mm) by 1.8 mils
(0.046 mm) thick), and the SentryGlas.RTM. Plus sheets (12 inches
by 12 inches (305 mm.times.305 mm) by 30 mils (0.75 mm) thick), are
conditioned at 23 percent relative humidity (RH), at a temperature
of 72 degrees F. overnight. The samples are laid up with a clear
annealed float glass plate layer (12 inches by 12 inches (305
mm.times.305 mm) by 2.5 mm thick), a decorated sheet layer from
above, a XIR.RTM.-75 Auto Blue V-1 film layer, a SentryGlas.RTM.
Plus sheet layer and a clear annealed float glass plate layer (12
inches by 12 inches (305 mm.times.305 mm) by 2.5 mm thick). The
glass/interlayer/glass assembly is then placed into a vacuum bag
and heated to 90-100 C for 30 minutes to remove any air contained
between the glass/interlayer/glass assembly. The
glass/interlayer/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/glass
laminate is removed from the autoclave.
EXAMPLE 6
[0126] Using the above mentioned ink set of Example 1, a 60 mil
thick (1.50 mm) SentryGlas.RTM. Plus sheet (a product of the DuPont
Company) is ink jet printed with a decoration with a NUR Tempo.RTM.
Modular Flatbed Inkjet Presses equipped to handle rigid sheet stock
manufactured by NUR Microprinters of Monnachie, N.J., to provide a
ink coverage of 300 percent.
[0127] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, and a Soft Look.RTM. UV/IR 25 solar
control film (a product of the Tomoegawa Paper Company, Ltd., of
Tokyo, Japan), are produced in the following manner. The decorated
sheets from above (12 inches by 12 inches (305 mm.times.305 mm)),
and the Soft Look.RTM. UV/IR 25 solar control films (12 inches by
12 inches (305 mm.times.305 mm)), are conditioned at 23 percent
relative humidity (RH), at a temperature of 72 degrees F.
overnight. The samples are laid up with a clear annealed float
glass plate layer (12 inches by 12 inches (305 mm.times.305 mm) by
2.5 mm thick), a decorated sheet layer from above, a Soft Look.RTM.
UV/IR 25 solar control film layer (with the coated surface of the
Soft Look.RTM. UV/IR 25 solar control film in contact with the
decorated sheet layer), a thin Teflon.RTM. film layer (12 inches by
12 inches (305 mm.times.305 mm)), and an annealed float glass layer
(12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm thick). The
glass/interlayer/Soft Look.RTM. UV/IR 25 solar control
film/Teflon.RTM. film/glass assembly is then placed into a vacuum
bag and heated to 90-100 C for 30 minutes to remove any air
contained between the glass/interlayer/Soft Look.RTM. UV/IR 25
solar control film/Teflon.RTM. film/glass assembly. The
glass/interlayer/Soft Look.RTM. UV/IR 25 solar control
film/Teflon.RTM. film/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/Soft
Look.RTM. UV/IR 25 solar control film/Teflon.RTM. film/glass
laminate is removed from the autoclave. Removal of the glass cover
sheet and the thin Teflon.RTM. film provides the glass/decorated
sheet/polyester film laminate of the present invention.
PREPARATIVE EXAMPLE PE 1
[0128] A plasticized poly(vinyl butyral) composition is prepared by
mixing a poly(vinyl butyral) with a hydroxyl number of 18.5 with a
plasticizer solution of tetraethylene glycol diheptanoate with 4
grams per liter of Tinuvin.RTM. P (a product of the Ciba Company),
1.2 grams per liter of Tinuvin.RTM. 123 (a product of the Ciba
Company), and 8 grams per liter of octylphenol and is extruded so
that the residence time in the extruder is within 10 to 25 minutes.
The feed ratio of the plasticizer to the dry poly(vinyl butyral)
flake is 46:100 (wt.:wt.). An aqueous solution of 3:1 potassium
acetate:magnesium acetate is injected during the extrusion to
deliver a potassium concentration of 50 to 100 ppm. The melt
temperature measured at the slot die is between 190 C and 215 C.
The molten sheet is quenched in a water bath. The self-supporting
sheet is passed through a dryer where excess water is allowed to
evaporate and then through a relaxer where "quenched in stresses"
are substantially relieved. The sheeting is then chilled to less
than 10 C, slit along the mid-point of the web width and then wound
up into rolls. The die lips at extrusion are adjusted to give the
sheeting immediately before slitting a flat cross-sectional
thickness profile. After slitting, two rolls of flat acoustic
poly(vinyl butyral) sheet are wound up into rolls. The average
thickness profile in each roll is 20 mils (0.51 mm). The roll width
is 1.12 meters.
EXAMPLE 7
[0129] A 90 mil thick (2.25 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 6-color CMYK+IcIm UV-curable
inkset and a UV-curable white ink available from NUR Microprinters
to provide a ink coverage of 500 percent.
[0130] A solution of A-1100 silane (0.05 weight percent based on
the total weight of the solution, a product of the Silquest
Company, believed to be gamma-aminopropyltrimethoxysilane),
isopropanol (66.63 weight percent based on the total weight of the
solution), and water (33.32 weight percent based on the total
weight of the solution), is prepared and allowed to sit for at
least one hour prior to use. A 12-inch by 12-inch piece of the
decorated SentryGlas.RTM. Plus sheet from above is dipped into the
silane solution (residence time of about 1 minute), removed and
allowed to drain and dry under ambient conditions.
[0131] Glass laminates composed of a glass layer, the silane primed
decorated sheet interlayer from above, a XIR.RTM.-75 Green film (a
product of the Southwall Company), the acoustic poly(vinyl butyral)
sheet from Preparative Example PE 1, above, and a glass layer are
produced in the following manner. The silane primed decorated
sheets from above (12 inches by 12 inches (305 mm.times.305 mm)),
the XIR.RTM.-75 Green films (12 inches by 12 inches (305
mm.times.305 mm) by 1.8 mils (0.046 mm) thick), and the sheets from
Preparative Example PE 1, above (12 inches by 12 inches (305
mm.times.305 mm) by 20 mils (0.51 mm) thick), are conditioned at 23
percent relative humidity (RH), at a temperature of 72 degrees F.
overnight. The samples are laid up with a clear annealed float
glass plate layer (12 inches by 12 inches (305 mm.times.305 mm) by
2.5 mm thick), a silane primed decorated sheet layer from above, a
XIR.RTM.-75 Green film layer, a sheet layer from Preparative
Example PE 1 from above and a clear annealed float glass plate
layer (12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm
thick). The glass/interlayer/glass assembly is then placed into a
vacuum bag and heated to 90-100 C for 30 minutes to remove any air
contained between the glass/interlayer/glass assembly. The
glass/interlayer/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/glass
laminate is removed from the autoclave.
EXAMPLE 8
[0132] A 120 mil thick (3.00 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 8-color CMYK+IcImIyIk
UV-curable inkset available from NUR Microprinters to provide a ink
coverage of 600 percent.
[0133] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, a SentryGlas.RTM. Plus sheet (a
product of the DuPont Company), and a RAYBARRIER.RTM. TFK-2583
solar control film (a product of the Sumitomo Osaka Cement
Company), are produced in the following manner. The decorated
sheets from above (12 inches by 12 inches (305 mm.times.305 mm)),
the SentryGlas.RTM. Plus sheet (12 inches by 12 inches (305
mm.times.305 mm) by 30 mils thick (0.75 mm)), and the
RAYBARRIER.RTM. TFK-2583 solar control film (12 inches by 12 inches
(305 mm.times.305 mm)), are conditioned at 23 percent relative
humidity (RH), at a temperature of 72 degrees F. overnight. The
samples are laid up with a clear annealed float glass plate layer
(12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm thick), a
decorated sheet layer from above, a SentryGlas.RTM. Plus sheet
layer, a RAYBARRIER.RTM. TFK-2583 solar control film layer (the
coated surface of the RAYBARRIER.RTM. TFK-2583 solar control film
in contact with the SentryGlas.RTM. Plus sheet), a thin Teflon.RTM.
film layer (12 inches by 12 inches (305 mm.times.305 mm)), and an
annealed float glass layer (12 inches by 12 inches (305
mm.times.305 mm) by 2.5 mm thick). The
glass/interlayer/RAYBARRIER.RTM. TFK-2583 film/Teflon.RTM.
film/glass assembly is then placed into a vacuum bag and heated to
90-100 C for 30 minutes to remove any air contained between the
glass/interlayer/RAYBARRIER.RTM. TFK-2583 film/Teflon.RTM.
film/glass assembly. The glass/interlayer/RAYBARRIER.RTM. TFK-2583
film/Teflon.RTM. film/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the
glass/interlayer/RAYBARRIER.RTM. TFK-2583 film/Teflon.RTM.
film/glass laminate is removed from the autoclave. Removal of the
glass cover sheet and the thin Teflon.RTM. film provides the
glass/decorated sheet/SentryGlas.RTM. Plus sheet/RAYBARRIER.RTM.
TFK-2583 film laminate of the present invention.
EXAMPLE 9
[0134] Using the above mentioned ink set of Example 1, a 30 mil
thick (0.75 mm) SentryGlas.RTM. Plus sheet (a product of the DuPont
Company) is ink jet printed with a decoration with a NUR Tempo.RTM.
Modular Flatbed Inkjet Presses equipped to handle rigid sheet stock
manufactured by NUR Microprinters of Monnachie, N.J., to provide a
ink coverage of 50 percent.
[0135] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, a SentryGlas.RTM. Plus sheet (a
product of the DuPont Company), a XIR.RTM.-70 HP film (a product of
the Southwall Company), an additional SentryGlas.RTM. Plus sheet
and a glass layer are produced in the following manner. The
decorated sheets from above (12 inches by 12 inches (305
mm.times.305 mm)), the XIR.RTM.-70 HP films (12 inches by 12 inches
(305 mm.times.305 mm) by 1 mil (0.026 mm) thick), and the
SentryGlas.RTM. Plus sheets (12 inches by 12 inches (305
mm.times.305 mm) by 30 mils (0.75 mm) thick), are conditioned at 23
percent relative humidity (RH), at a temperature of 72 degrees F.
overnight. The samples are laid up with a clear annealed float
glass plate layer (12 inches by 12 inches (305 mm.times.305 mm) by
2.5 mm thick), a decorated sheet layer from above, a
SentryGlas.RTM. Plus sheet layer, a XIR.RTM.-70 HP film layer, a
SentryGlas.RTM. Plus sheet layer and a clear annealed float glass
plate layer (12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm
thick). The glass/interlayer/glass assembly is then placed into a
vacuum bag and heated to 90-100 C for 30 minutes to remove any air
contained between the glass/interlayer/glass assembly. The
glass/interlayer/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/glass
laminate is removed from the autoclave.
EXAMPLE 10
[0136] A 60 mil thick (1.50 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 4-color CMYK UV-curable
inkset available from NUR Microprinters to provide a ink coverage
of 100 percent.
[0137] A solution of A-1100 silane (0.05 weight percent based on
the total weight of the solution, a product of the Silquest
Company, believed to be gamma-aminopropyltrimethoxysilane),
isopropanol (66.63 weight percent based on the total weight of the
solution), and water (33.32 weight percent based on the total
weight of the solution), is prepared and allowed to sit for at
least one hour prior to use. A 12-inch by 12-inch piece of the
decorated SentryGlas.RTM. Plus sheet from above is dipped into the
silane solution (residence time of about 1 minute), removed and
allowed to drain and dry under ambient conditions.
[0138] Glass laminates composed of a glass layer, the silane primed
decorated sheet interlayer from above, a SentryGlas.RTM. Plus sheet
(a product of the DuPont Company), and a XIR.RTM.-70 HP Auto film
(a product of the Southwall Company), are produced in the following
manner. The silane primed decorated sheets from above (12 inches by
12 inches (305 mm.times.305 mm)), the SentryGlas.RTM. Plus sheet
(12 inches by 12 inches (305 mm.times.305 mm) by 60 mils thick
(1.50 mm)), and the XIR.RTM.-70 HP Auto films ((12 inches by 12
inches (305 mm.times.305 mm) by 2 mils (0.05 mm) thick), are
conditioned at 23 percent relative humidity (RH), at a temperature
of 72 degrees F. overnight. The samples are laid up with a clear
annealed float glass plate layer (12 inches by 12 inches (305
mm.times.305 mm) by 2.5 mm thick), a silane primed decorated sheet
layer from above, a SentryGlas.RTM. Plus sheet layer, a XIR.RTM.-70
HP Auto film layer (metallized surface of the XIR.RTM.-70 HP Auto
film in contact with the SentryGlas.RTM. Plus sheet), a thin
Teflon.RTM. film layer (12 inches by 12 inches (305 mm.times.305
mm)), and an annealed float glass layer (12 inches by 12 inches
(305 mm.times.305 mm) by 2.5 mm thick). The
glass/interlayer/XIR.RTM.-70 HP Auto film/Teflon.RTM. film/glass
assembly is then placed into a vacuum bag and heated to 90-100 C
for 30 minutes to remove any air contained between the
glass/interlayer/XIR.RTM.-70 HP Auto film/Teflon.RTM. film/glass
assembly. The glass/interlayer/XIR.RTM.-70 HP Auto film/Teflon.RTM.
film/glass pre-press assembly is then subjected to autoclaving at
135 C for 30 minutes in an air autoclave to a pressure of 200 psig
(14.3 bar), as described above. The air is then cooled while no
more air is added to the autoclave. After 20 minutes of cooling
when the air temperature is less than about 50 C, the excess
pressure is vented, and the glass/interlayer/XIR.RTM.-70 HP Auto
film/Teflon.RTM. film/glass laminate is removed from the autoclave.
Removal of the glass cover sheet and the thin Teflon.RTM. film
provides the glass/decorated sheet/SentryGlas.RTM. Plus
sheet/XIR.RTM.-70 HP Auto film laminate of the present
invention.
EXAMPLE 11
[0139] A 90 mil thick (2.25 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 6-color CMYK+IcIm UV-curable
inkset and a UV-curable white ink available from NUR Microprinters
to provide a ink coverage of 300 percent.
[0140] A solution of A-1100 silane (0.05 weight percent based on
the total weight of the solution, a product of the Silquest
Company, believed to be gamma-aminopropyltrimethoxysilane), acetic
acid (0.01 weight percent based on the total weight of the
solution), isopropanol (66.63 weight percent based on the total
weight of the solution), and water (33.31 weight percent based on
the total weight of the solution), is prepared. A 12-inch by
12-inch piece of the decorated SentryGlas.RTM. Plus sheet from
above is dipped into the silane solution (residence time of about 1
minute), removed and allowed to drain and dry under ambient
conditions.
[0141] Glass laminates composed of a glass layer, the silane primed
decorated sheet interlayer from above, a SentryGlas.RTM. Plus sheet
(a product of the DuPont Company), a XIR.RTM.-70 HP film (a product
of the Southwall Company), an additional SentryGlas.RTM. Plus sheet
and a glass layer are produced in the following manner. The silane
primed decorated sheets from above (12 inches by 12 inches (305
mm.times.305 mm)), the XIR.RTM.-70 HP films (12 inches by 12 inches
(305 mm.times.305 mm) by 1 mil (0.026 mm) thick), and the
SentryGlas.RTM. Plus sheets (12 inches by 12 inches (305
mm.times.305 mm) by 30 mils (0.75 mm) thick), are conditioned at 23
percent relative humidity (RH), at a temperature of 72 degrees F.
overnight. The samples are laid up with a clear annealed float
glass plate layer (12 inches by 12 inches (305 mm.times.305 mm) by
2.5 mm thick), a silane primed decorated sheet layer from above, a
SentryGlas.RTM. Plus sheet layer, a XIR.RTM.-70 HP film layer, a
SentryGlas.RTM. Plus sheet layer and a clear annealed float glass
plate layer (12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm
thick). The glass/interlayer/glass assembly is then placed into a
vacuum bag and heated to 90-100 C for 30 minutes to remove any air
contained between the glass/interlayer/glass assembly. The
glass/interlayer/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/glass
laminate is removed from the autoclave.
EXAMPLE 12
[0142] A 120 mil thick (3.00 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 8-color CMYK+IcImIyIk
UV-curable inkset available from NUR Microprinters to provide a ink
coverage of 600 percent.
[0143] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, a XIR.RTM.-75 Auto Blue V-1 film (a
product of the Southwall Company), a Butacite.RTM. poly(vinyl
butyral) sheet (a product of the DuPont Company), and a glass layer
are produced in the following manner. The decorated sheets from
above (12 inches by 12 inches (305 mm.times.305 mm)), the
XIR.RTM.-75 Auto Blue V-1 films (12 inches by 12 inches (305
mm.times.305 mm) by 1.8 mils (0.046 mm) thick), and the
Butacite.RTM. poly(vinyl butyral) sheets (12 inches by 12 inches
(305 mm.times.305 mm) by 30 mils (0.75 mm) thick), are conditioned
at 23 percent relative humidity (RH), at a temperature of 72
degrees F. overnight. The samples are laid up with a clear annealed
float glass plate layer (12 inches by 12 inches (305 mm.times.305
mm) by 2.5 mm thick), a decorated sheet layer from above, a
XIR.RTM.-75 Auto Blue V-1 film layer, a Butacite.RTM. poly(vinyl
butyral) sheet layer and a clear annealed float glass plate layer
(12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm thick). The
glass/interlayer/glass assembly is then placed into a vacuum bag
and heated to 90-100 C for 30 minutes to remove any air contained
between the glass/interlayer/glass assembly. The
glass/interlayer/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/glass
laminate is removed from the autoclave.
EXAMPLE 13
[0144] Using the above mentioned ink set of Example 1, a 60 mil
thick (1.50 mm) SentryGlas.RTM. Plus sheet (a product of the DuPont
Company) is ink jet printed with a decoration with a NUR Tempo.RTM.
Modular Flatbed Inkjet Presses equipped to handle rigid sheet stock
manufactured by NUR Microprinters of Monnachie, N.J., to provide a
ink coverage of 150 percent.
[0145] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, a XIR.RTM.-70 HP film (a product of
the Southwall Company), a SentryGlas.RTM. Plus sheet (a product of
the DuPont Company), and a glass layer are produced in the
following manner. The decorated sheets from above (12 inches by 12
inches (305 mm.times.305 mm)), the XIR.RTM.-70 HP films (12 inches
by 12 inches (305 mm.times.305 mm) by 1 mil (0.026 mm) thick), and
the SentryGlas.RTM. Plus sheets (12 inches by 12 inches (305
mm.times.305 mm) by 30 mils (0.75 mm) thick), are conditioned at 23
percent relative humidity (RH), at a temperature of 72 degrees F.
overnight. The samples are laid up with a clear annealed float
glass plate layer (12 inches by 12 inches (305 mm.times.305 mm) by
2.5 mm thick), a decorated sheet layer from above, a XIR.RTM.-70 HP
film layer, a SentryGlas.RTM. Plus sheet layer and a clear annealed
float glass plate layer (12 inches by 12 inches (305 mm.times.305
mm) by 2.5 mm thick). The glass/interlayer/glass assembly is then
placed into a vacuum bag and heated to 90-100 C for 30 minutes to
remove any air contained between the glass/interlayer/glass
assembly. The glass/interlayer/glass pre-press assembly is then
subjected to autoclaving at 135 C for 30 minutes in an air
autoclave to a pressure of 200 psig (14.3 bar), as described above.
The air is then cooled while no more air is added to the autoclave.
After 20 minutes of cooling when the air temperature is less than
about 50 C, the excess pressure is vented, and the
glass/interlayer/glass laminate is removed from the autoclave.
EXAMPLE 14
[0146] A 90 mil thick (2.25 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 4-color CMYK UV-curable
inkset and a UV-curable white ink available from NUR Microprinters
to provide a ink coverage of 100 percent.
[0147] Glass laminates composed of a glass layer, the decorated
sheet interlayer from above, a XIR.RTM.-70 HP film (a product of
the Southwall Company), an Evasafe.RTM. ethylene vinyl acetate
sheet (a product of the Bridgestone Company), and a glass layer are
produced in the following manner. The decorated sheets from above
(12 inches by 12 inches (305 mm.times.305 mm)), the XIR.RTM.-70 HP
films (12 inches by 12 inches (305 mm.times.305 mm) by 1 mil (0.026
mm) thick), and the Evasafe.RTM. ethylene vinyl acetate sheets (12
inches by 12 inches (305 mm.times.305 mm) by 15 mils (0.38 mm)
thick), are conditioned at 23 percent relative humidity (RH), at a
temperature of 72 degrees F. overnight. The samples are laid up
with a clear annealed float glass plate layer (12 inches by 12
inches (305 mm.times.305 mm) by 2.5 mm thick), a decorated sheet
layer from above, a XIR.RTM. 70 HP film layer, a Evasafe.RTM.
ethylene vinyl acetate sheet layer and a clear annealed float glass
plate layer (12 inches by 12 inches (305 mm.times.305 mm) by 2.5 mm
thick). The glass/interlayer/glass assembly is then placed into a
vacuum bag and heated to 90-100 C for 30 minutes to remove any air
contained between the glass/interlayer/glass assembly. The
glass/interlayer/glass pre-press assembly is then subjected to
autoclaving at 135 C for 30 minutes in an air autoclave to a
pressure of 200 psig (14.3 bar), as described above. The air is
then cooled while no more air is added to the autoclave. After 20
minutes of cooling when the air temperature is less than about 50
C, the excess pressure is vented, and the glass/interlayer/glass
laminate is removed from the autoclave.
EXAMPLE 15
[0148] A 30 mil thick (0.75 mm) SentryGlas.RTM. Plus sheet (a
product of the DuPont Company) is ink jet printed with a decoration
with a NUR Tempo.RTM. Modular Flatbed Inkjet Presses equipped to
handle rigid sheet stock manufactured by NUR Microprinters of
Monnachie, N.J., utilizing a pigmented 8-color CMYK+IcImIyIk
UV-curable inkset available from NUR Microprinters to provide a ink
coverage of 400 percent.
[0149] Glass laminates composed of a Solex.RTM. green glass layer,
the decorated sheet interlayer from above, a XIR.RTM.-70 HP film (a
product of the Southwall Company), a SentryGlas.RTM. Plus sheet (a
product of the DuPont Company), and a glass layer are produced in
the following manner. The decorated sheets from above (12 inches by
12 inches (305 mm.times.305 mm)), the XIR.RTM.-70 HP films (12
inches by 12 inches (305 mm.times.305 mm) by 1 mil (0.026 mm)
thick), and the SentryGlas.RTM. Plus sheets (12 inches by 12 inches
(305 mm.times.305 mm) by 30 mils (0.75 mm) thick), are conditioned
at 23 percent relative humidity (RH), at a temperature of 72
degrees F. overnight. The samples are laid up with a Solex.RTM.
green glass plate layer (12 inches by 12 inches (305 mm.times.305
mm) by 2.5 mm thick), a decorated sheet layer from above, a
XIR.RTM.-70 HP film layer, a SentryGlas.RTM. Plus sheet layer and a
clear annealed float glass plate layer (12 inches by 12 inches (305
mm.times.305 mm) by 2.5 mm thick). The green glass/interlayer/glass
assembly is then placed into a vacuum bag and heated to 90-100 C
for 30 minutes to remove any air contained between the green
glass/interlayer/glass assembly. The green glass/interlayer/glass
pre-press assembly is then subjected to autoclaving at 135 C for 30
minutes in an air autoclave to a pressure of 200 psig (14.3 bar),
as described above. The air is then cooled while no more air is
added to the autoclave. After 20 minutes of cooling when the air
temperature is less than about 50 C, the excess pressure is vented,
and the green glass/interlayer/glass laminate is removed from the
autoclave.
[0150] While certain of the preferred embodiments of the present
invention have been described and specifically exemplified above,
it is not intended that the invention be limited to such
embodiments. Various modifications may be made without departing
from the scope and spirit of the present invention, as set forth in
the following claims.
* * * * *